Embed Size (px)
Citation preview
P1-Mo
ATTEMPTS TO OBTAIN OPTICALLY ACTIVE TRIFLOROMETHYL ARYL SULFOXIDES
VIA RESOLUTIONS OF THE RACE MATES.
Jozef Drabowicz,a Jerzy Luczak,a Marian Mikolajczyk,a Natasza V.Kondratenko,b Lew M.Yagupolskib
aCenter of Molecular and Macromolecular Studies, Polish Academy of
Sciences, Department of Heteroorganic Chemistry, 90-363 Lodz, Sienkiewicza 112, Poland
bInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, 02094 Kiev, Murmanskaya Str. 5, Ukraine
The presence of perfluoroalkyl chains in the sulfoxide structure creates from optically active compounds a very interesting group of chiral sulfinyl derivatives. To the best of our knowledge this kinds of sulfoxides have not been so far reported as optically active species. Only recently one of our groups has reported the first successful attempts to prepare optically active trifluoromethyl aryl sulfoxides based on asymmetric oxidation of the corresponding sulfides.1 In this communication we would like do disclose the preliminary results of testing protocols for their preparation as optically active species based on:
a) the oxidative kinetic resolution of the corresponding racemic trifluoromethyl aryl sulfoxides,
b) the optical resolution of racemic mixtures via complexation with β-cyclodextrin or other optically active “host” molecules or by HPLC chromatography on chiral columns.
In this context it is interesting to note that recently a few racemic (α-
arylsulfinyl)difluoroacetic acids, Ar(S(O)CF2COOH, have been partially resolved by the Kiev group via their diastereomeric salts with optically active α-methylbenzylamine.2
[1] J.Drabowicz, J.Luczak, M.Mikolajczyk, a communication to be presented at the 14th
European Symposium on Fluorine Chemistry, July 11-16, 2004, Poznan, Poland. [2] A.V.Matsnev, N.V.Kondratenko, Y.L.Yagupolskii, L.M.Yagupolskii, Tetrahedron Lett.,
43, 2949 (2002).
99
P2-Mo
UNEXPECTED FORMATION OF 2-VINYLTHIIRANE IN THE REACTION OF ADAMANTANETHIONE
WITH LITHIATED METHOXYALLENE
Grzegorz Mloston*1), Robert Schütz2) , Hans-Ulrich Reissig2)
1)University of Lodz, Section of Heteroorganic Compounds, Narutowicza 68, PL-90-136 Lodz; e-mail: [email protected]
2) Free University Berlin, Inst. Org. Chem., Takustr. 3, D-14195 Berlin Adamantanthione (1) is easily available from adamantanone and can be stored at ambient conditions for a longer period of time; for these reasons it is frequently explored as a model thioketone to test the reactivity of the C=S bond [1]. Reactions of 1 with organometallic nucleophiles such as Grignard reagents are reported to occur regioselectively leading to the formation of a C-C bond (carbophilic attack) [2]. However, some experimental details like the influence of the solvent seem to need further investigation. Lithiated alkoxyallenes are versatile reagents [3, 4] for preparation of heterocyclic compounds but their reactions with thioketones have not been reported yet. Treatment of 1-methoxyallene with n-BuLi in THF solution at -50 oC affords the lithiated derivative 2 which smoothly decolorizes 1 at -20 oC to give a thiolate salt. Subsequent treatment of this salt with methyl iodide at rt leads to sulfane 3.
S
H2C=C=C(Li)OMe
SMe
OMe
S
OMe
1 2 3 4
.
On the other hand, quenching of the thiolate solution with water results in the exclusive formation of vinylthiirane 4. Both results indicate that the addition of the lithiated methoxyallene 2 to 1 follows the carbophilic pathway. Spontaneous 1,3-cyclization of the organosulfane obtained after hydrolysis differs remarkably from processes observed with similar allenyl amines or alcohols which regioselectively undergo 1,5-cyclization yielding pyrrole or furane derivatives, respectively [4]. Some preliminary results obtained with 2 and aromatic thioketones will also be presented. The structures of isolated products were clearly confirmed by means of spectroscopic methods. ------------------------- G. M. thanks the Alexander von Humboldt Stiftung for generous support.
100
[1] H. Heimgartner, G. Mloston, J. Romanski, Electronic Encyclopedia of Reagents for Organic Synthesis, Ed. L. Paquett, J. Willey & Sons, New York 2004; [2] D. Paquer, M. Vazeux, J. Organomet. Chem., 1977, 140, 257 ; V. Rautenstrauch, Helv. Chim. Acta 1974, 57, 496; [3] L. Brandsma, N. A. Nedolya, Synthesis 2004, 735. [4] H.-U. Reissig et al., J. Heterocyclic Chem., 2000, 37, 597.
P3-Mo
STRUCTURAL AND SPECTRAL PROPERTIES OF STABLE SULFENATE AND SELENENATE ANIONS
Keiichi Shimada,a Kei Goto,a Takayuki Kawashima,a
Kazuya Ishimura,b Nozomi Takagib and Shigeru Nagaseb
aDepartment of Chemistry, Graduate School of Science, The University of Tokyo. 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (JAPAN)
bDepartment of Theoretical Studies, Institute for Molecular Science, Myodaiji, Okazaki 444-8585 (JAPAN)
Sulfenate anions (R-SO–) have been recognized as important intermediates in the organosulfur chemistry, and selenenate anions (R-SeO–) have been attracting attention as the selenium analogues of sulfenate anions. However, because of their instability, only limited data have been accumulated on the structural and spectral properties of these species. Here we report the syntheses of stable alkali selenenates bearing a bowl-type steric protection group (denoted as Bpq) along with the comparison between the structural and spectral properties of selenenates 2a,b and sulfenates 3a,b.
The reaction of selenenic acid 1 with potassium hydride in the presence of 18-crown-6 or cryptand[2.2.2] afforded the corresponding selenenate potassium salts 2a or 2b, both of which were isolated as stable brown crystals. X-ray crystallographic analysis established the structures of 2a and 2b. The 13C NMR data of 2 and 3 suggested that the electronic delocalization from the chalcogenate moiety to the benzene ring is more significant in the sulfenates than in the selenenates. The theoretical study on the structures and spectral properties of the sulfenates and selenenates will also be described.
X
≡ BpqX
1: X = SeOH2a: X = SeO–K+·18-crown-62b: X = SeO–K+·cryptand[2.2.2]3a: X = SO–K+·18-crown-63b: X = SO– K+·cryptand[2.2.2]
101
P4-Mo
EXPERIMENTAL AND THEORETICAL STUDIES OF RADICAL INTERMEDIATE REACTIVITY DURING THE REDUCTION OF
DITHIOLETHIONES AND THE CORRESPONDING DITHIOLIUM CATIONS
Marie-Laurence Abasq1, Jean-Louis Burgot1, André Darchen2, Eric Furet3,
Mokhtar Saidi4
1Laboratoire de Chimie Analytique. U.F.R des Sciences Pharmaceutiques. Université de Rennes I. 35043 Rennes cedex (FRANCE). 2Laboratoire de
Physicochimie. ENSCR. 35700 Rennes (FRANCE). 3Laboratoire de Chimie du Solide et Inorganique Moléculaire. UMR CNRS 6511. ENSCR. 35700 Rennes (FRANCE). 4Université de Ouargla. Route de Ghardaïa. 30000
Ouargla (ALGERIE) [email protected]
It is interesting to investigate the formation of intermediates during
the reduction of 1,2-dithiole-3-thiones 1 since these molecules are known for their antioxidant and radical scavenger activities. These properties may be implicated in the new therapeutic use of Sulfarlem (1a; R4 = H, R5 = p.CH3O-C6H4) as a chemopreventive agent of lung cancer1. The electrochemical behaviour of numerous 1,2-dithiole-3-thiones has already received some attention contrary to that of the S-alkylated derivatives of 1, 3-methylsulfanyl-1,2-dithiolium cations 2 which are intermediates in the metabolism of 1. The electrochemical reduction of some 1,2-dithiolium cations has already show the occurrence of a radical dimerisation2 .
SS
R
R S4
5
1 23
45
54
321
5
4
SS
R
R S 3CH+
1 2
In this work, the electrochemical behaviour of some compounds 1 and 2 was studied in DMF. At Pt or C electrodes, in all cases the reduction was the result of two competitive pathways: an ECE process with ring opening and a dimerisation of an intermediate radical. Theoretical calculations by means of DFT have been carried out in order to contribute to the reactivity of the radical intermediate in the reduction of 1 and 2. [1] S. Lam, C. Macaulay, J.C. Leriche, Y. Dyachkova, A. Coldman, M. Guillaud, E. Hawk, M.O. Christen and A.F. Gadzar PCT Int. Appl. 2003 WO 2003068219. [2] K. Bechgaard, V.N. Parker, C.T. Pedersen J. Amer. Chem. Soc. 1973, 95, 4373-4378.
102
P5-Mo
ASSIGNEMENTS OF HYPERFINE SPLITTINGS BY DFT METHODS OF RADICALS CONTAINING 33S (I = 3/2), 31P (I = 1/2 )
AND 29Si (I = 1/2), NUCLEI.
L. Hermosilla, P. Calle, and C. Sieiro.
Departamento de Química Física Aplicada. Facultad de Ciencias. Universidad Autónoma de Madrid. 28049- Madrid (Spain)
The assignment of the hyperfine splittings (hfs) obtained by analysis of EPR (Electron Paramagnetic Resonance) spectra, is a basic task in this magnetic spectroscopy. At present, post HF methodologies, that is, correlated ab initio molecular orbital methods, such as Multireference Configuration Interaction (MRCI), Quadruple Configuration Interaction (QCI) or Coupled Cluster (CC) techniques, are the most promising theoretical techniques to obtain this EPR magnetic parameter with a high level of precision. However, the computational time cost is completely forbidden in the case of medium and large size radicals, and therefore, they are only adequate for the analysis of very small systems. Recently, the Density Functional Theory (DFT) methodology is giving accurate values of spin densities and is allowing good assignments of experimental hfs1-4. The use of these DFT methods allows to carry out calculations with lower CPU time cost using the same basis respect to other post-HF methods.
The basic aim of the present work is to carry out a complete analysis about the predictive power of several hybrid functionals in predicting the isotropic hyperfine coupling constants of organometallic radicals containing 29Si (I = 1/2), 31P (I = 1/2), and 33S (I = 3/2) nuclei. Neutral, anions and cations radicals are analysed, ranging from small diatomic radicals till medium and large size systems, and considering different hybrid functionals and different basis sets. The hfs for the radicals studied are compared with experimental data obtaining a good correlation. 1. Batra, R.; Giese, B.; Spichty, M.; Gescheidt, G.; Houk, K. N. J. Phys. Chem. 1996, 100, 18371. 2. Nguyen, M. T.; Creve, S.; Eriksson, L. A.; Vanquickenborne, L. G. Mol. Phys., 1997, 91, 537.
3. Janoschek, R. Pure Appl. Chem. 2001, 73, 1521. 4. Hermosilla, L.; Calle, P. García de la Vega, J. M.; Sieiro, C. To be published.
This work has been supported by the Grant: BQU2002-00582 (DGICyT).
103
P6-Mo
THEORETICAL STUDY OF THE MECHANISM OF NEW THIAZOLONE STRUCTURE .
Y.Akacema, N.Achouia, M. Amari(b) and B. Kolli(b) .
a Laboratory of Thermodynamic and Theoretical Chemistry .University U.S.T.H.B,
Algiers, Algeria b Laboratory of Structural Organic Chemistry .University U.S.T.H.B,
Algiers, Algeria E.mail : [email protected]
The group as NH-CS-NH- occurs in numerous biologically active compounds. In recent years much attention has been focused on the development of these compounds which are useful in Synthetic Chemistry and in Pharmacology. The cycloadditions between maleimide and thiourea realized by B. Kolli and all., gives the thiazolone structure. With the development of improved algorithms and increased computational facilities, the geometrical structures energies, vibrational frequencies and atomic charges can be now studied with the quantum chemical methods. So, we are interested to realize a theoretical study of the mechanism of the thiazolone synthesis. We are describe the reaction mechanism by the reaction pathway technique . Semi-empiric methods (AM1, PM3 ) as well as the hybrid density functional B3LYP methods have been employed. The 6-31G* basis set is used and all calculations are carried out with the Gaussian 98 program. For all the structures considered in this study, the results obtained from, have been compared to the experimental data available in the literature. Our theoretical results prove and complete the experiments results.
104
P7-Mo
NEW BIFUNCTIONAL SULFUROUS-SILICON PODANDS
Bogusława Łęska, Błażej Gierczyk, Bogumił Brzezinski and Grzegorz Schroeder
Faculty of Chemistry, A. Mickiewicz University, Grunwaldzka 6,
60-780 Poznań, Poland e-mail: [email protected]
Podands are very important compounds in chemistry. The inorganic
esters of poloxaethylene glycols formed a new class of materials for laboratories and industry. A low price of podands and properties like as crown ethers or cryptands determined their application. For the synthesis this group of podands polyoxaethylene glycols are very good starting materials. Now we want to present the results of new part of our podand studies. Trisalkoxy derivatives of (3-mercaptopropyl)-trimethoxysilane was obtained by transesterification reaction.
R = CH (OCH CH ) ; CH CH ; CH 3 2 2 n 3 2 3
Si
RO
RO
RO SH
In a presence of proton, ions or small organic molecules, Si-podands with CH3(OCH2CH2)n substituents act as molecular channels, in which an ion migrates inside atomic cavity.
Owing to a development of systems with molecular channels through functional group S-H, it is possible not only an electrodeposition (Ag, Au), but also an association with bioorganic molecules. It produces new possibilities of ion channel examination.
The presenting results have included spectroscopic, electrochemical and kinetic studies and also theoretical calculations for those bifunctional S - Si-podands and theirs complexes.
105
P8-Mo
PREPARATION AND DETERMINATION OF 4,8-DIETHYLBENZO- [1,2-d:4,5-d’]BIS[1,2,3]TRITHIOLE DICATION [DEBBT(2+)]
Takeshi Kimura,
SS
S SS
S
Et
Et
mCPBAS
SS
Et
Et
SS
S
O
D2SO4
SS
SSS
S
Et
Et DSO4-
D2SO4
SS
SEt
Et
SS
S2DSO4
-
D2SO4
-D2O SS
SEt
Et
SS
S2DSO4
-
DEBBT(2+)-S
¥+
DEBBT(¥+)
DEBBT 1-O
+
+
DEBBT(2+)
2+
DEBBT
Takashi Sasaki, Hiroaki Yamaki, and Eiich Suzuki†
Center for Instrumental Analysis, Iwate University, Morioka, Iwate 020-8551 Japan; †Department of Chemical Engineering, Iwate University,
Morioka, Iwate 020-8551 Japan
DEBBT was oxidized using concd D2SO4, leading to the generation of radical cation DEBBT(•+). DEBBT(•+) in the solution was further oxidized to produce dication DEBBT(2+), as determined by 1H and 13C-NMR. DEBBT(2+) was also prepared by treating DEBBT 1-oxide with concd D2SO4, and was verified by 1H and 13C-NMR. The 13C-NMR chemical shifts of DEBBT(2+), calculated by the DFT method at the B3LYP6-31G** level, correlated well with those obtained experimentally.
The ESR signal of DEBBT(2+) generated from DEBBT 1-O was
observed in the solution, which implies that singlet-state dication DEBBT(2+)-S isomerizes to triplet-state dication DEBBT(2+)-T, and that two molecules of DEBBT(2+)-T further form a spin pair at one trithiole ring with sufficient distance between the two radical centers. The oxidation of DEBBT with one or two equivalents of single-electron oxidizing reagents produced DEBBT(•+) and DEBBT(2+), and the salts were isolated into a stable form. However, the DEBBT(2+) that was prepared by oxidation with NOPF6 proved silent for NMR in CD3CN, while ESR is active.
106
P9-Mo
NOVEL COPPER (I) COMPLEXES AND CLUSTERS WITH PHOSPHORUS-SULFUR AND SULFUR-SULFUR
CONTAINING LIGANDS
Lidiya I.Kursheva, Olga N.Kataeva, Dmitrii B.Krivolapov, Elvira S.Batyeva, O.G.Sinyashin
A.E.Arbuzov Institute of Organic & Physical Chemistry, Arbuzov Str.8,
420088 Kazan, Russia Fax:+7 8432 73-22-53; e-mail: [email protected]
Over the past few years we have been studing the coordination of thioderivatives of P(III) with copper(I) halides. In this context, the complexation of thiophosphites and thiophosphonites with CuX (X -/Cl, Br, I) has been investigated. The following complexes with ligands containing P-S- and P-S, P-C-bonds have been synthesized and characterized by X-ray single crystal diffraction: CuX•L [L -/ P(n-Alk S)3, P(i-PrS)3, P(i-PrS)2(Cl), P(t-Bu)(SEt)2, P(Ph)(SEt)2, P(Ph)(SEt)(Cl)]. Copper(I) halides are notable for their ability to form the variety of structures and coordination modes with these ligands depending on their nature and volume: rhomboid Cu2X2 dimers and Cu4X4 cubane tetramers with monodentate type of coordination being more favorable for bulky ligands; (Cu2X2)n stair step polymers and (CuX)n chains with bi- or tridentate type of coordination. We have found that these coordination compounds may undergo the transformation in coordination sphere of metal. As the result the copper clusters including P-S- or S-S - ligands have arised. The X-ray crystal structure of complex containing P-S-ligands, [(Cu4Cl4• (P(i-PrS)3)], is composed of two dimensional nets consisting of Cu8Cl8 clusters. The tridentate coordination mode via Cu-P and Cu-S -bonds has been observed in this compound. The structure of complexes including S-S -ligands (disulfides) are of the type CuX•L [L- (EtS)2, (i-PrS)2; X- Cl,Br] with bidentate coordination via Cu-S-bonds. Their crystal structure is a polymeric cluster [CuX(RS)2]n formed by Cu2X2 rings with fused S-S containing cycles.
Authors thank the Russian Foundation for Basic Research 03-03-33076 and Program 7 of the Division of Chemistry and Material Science of the Russian Academy of Sciences (RAS) for support.
107
P10-Mo
FORMATION OF 5-[(1-ALKOXYALKYLIDENE)AMMONIO]ALKYL-
THIANTHRENIUM- AND 5-[(1-ALKYLTHIOALKYLIDENE) -AMMONIO] ALKYLTHIANTHRENIUM SALTS
Henry. J. Shine and Bingjun Zhao
Department of Chemistry and Biochemistry, Texas Tech University,
Lubbock, Texas, 79409-1061, U. S. A [email protected].
5,10-Thianthreniumdiylalkane salts (2) are formed by addition of thianthrene cation radical salts (1) to alkenes in nitrile solvents (RCN), eq. 1. In some cases, if a small amount of an alcohol (R´OH) is present prior to
S
S SS
X
2D
CBA
2XS
S1 2
RCN(1)
C
A
D
B
reaction, not only 2 but also a new product, a 5-[(1-alkoxyalkylidene)- ammonio]alkylthianthrenium salt (3), is formed, comprised of four components, thianthrene, alkene, solvent and alcohol, eq. 2. The reaction
C
NH
D
A B
CR OR'
SS 2X
1 +RCN
R'OH
3
(2)C
A
D
B
is limited to those alkenes in which A and D are small alkyl groups (Me, Et), B is Me or H, and C is H. Compounds 3 can also be formed by the decomposition of 2 in RCN containing R´OH. We believe that 3 is formed in each circumstance by the spontaneous, slow opening of 2 and successive reactions with RCN and R´OH (Scheme 1). Analogous reactions were carried out with some alkyl thiols (R´SH) in place of an alcohol.
C
N
D
A B
C
SB2A
D3
RCN R'OH
X = ClO4 PF6,
S
Scheme 1CR
108
P11-Mo
An ab initio molecular orbital study of structural isomers of dithioopyrrolopyrrole
Farahnaz Nourmohammadiana , Issa Yavarib, siamak salami, Alireza
Mihabibia
aDepartment of Colorant Manufacture, Iran Color Research Center, PO Box: 1665618481, Tehran, Iran, [email protected]
aDepartment of Chemistry, University of Tarbiat Modarres, Tehran, Iran
The thiocarbonyl group, -C=S, occurs in a wide range of compounds, although the simpler thioketone and thioaldehyde systems appear to be unstable. Dithiopyrrolopyrroles are important pigments, for example dithio-3, 6-diphenyl pyrrolopyrrole are used for optical recording and storage of information in the form of bits1-2 but there aren’t many research about them. Even though dithiopyrrolopyrrole structural isomers are not presently available for more studies, it is possible to carry out ab initio calculations at the Hartree-Fock, and DFT level, from which many properties and structures can be obtained with an accuracy that is competitive with experiment. In this communication, ab initio molecular orbital calculations at HF/6-31G*, HF/6-311+G**, B3LYP/6-31G* and B3LYP/6-311+G** levels of theory for geometry optimization are reported for 1,4-dithio-pyrrolo[3,4-c]pyrrole (DtPP, 1) and towelve structural isomers of dithiopyrrolopyrroles. Three isomers include 2 C=CH and 2 NH-CS units. Four structural isomers include 2 C=CH units, together with 2 NH and 2 C=S groups. Six Isomers possess 2 CH, 2 C, 2 NH, and 2 C=S fragments. The most interesting conclusion from the calculation is that three isomers are more stable than DtPP 1.
Dithiopyrrolopyrroles, 1 [1] U.S. Pat. No. 5, 500, 314, 1996. [2] U.S. Pat. No. 4,632,893, 1986.
109
P12-Mo
SPECTROSCOPIC AND THEORETICAL STUDIESOF SOME META- AND PARA- SUBSTITUTED α-METHYLSULFINYL-
α-DIETHOXYPHOSPHORYL ACETOPHENONES
Paulo R. Olivatoa, Adriana K. C. A. Reis, a Alessandro Rodriguesa, Julio Zukerman-Schpectorb, Claudio F. Tormenac and Maurizio Dal Colled
aInstituto de Química, Universidade de São Paulo, C.P. 26077, CEP 05513-970, São Paulo, SP; bDepartamento de Química, UFSCAR, São Carlos, SP; cDepartamento de Química, FFCLRP-USP, Ribeirão Preto , SP , Brazil; dDipartimento di Chimica, Università di Ferrara, Ferrara, Italy
The νCO IR data of some meta- and para-substituted α-methylsulfinyl- α-diethoxyphosphorylacetophenones(I) along with DFT/6-31G** computations of (Ic) have shown both in solution of solvents of increasing polarity and in the gas phase the existence of two pairs of diasteromers (racemic mixture).
P
S
OO
OO
O
Y
(I)
Y = OMe (a), Me (b), H (c), F (d), Cl (e), Br (f) e and NO2 (g)
*
*
The more stable and less polar (CSSS; CRSR) diastereomer pair display the [MeS(O)] group in a quasi-periplanar conformation and the [P(O)(OEt)2] group in a anti-clinal conformation relative to the carbonyl group. The less stable and more polar (CRSS; CSSR) diastereomer pair presents both substituents in a syn- clinal conformation. The observed solvent effect both on the νCO doublet components and on the two 1H NMR MeS(O) methyl signals in the whole series along with the complete exchange of the α-methyne hydrogen atom of the meta-(Ia) derivative by deuterium of the D2O in neutral chloroform solution strongly indicate that both pairs of diastereomers [(CSSS; CRSR) and (CRSS; CSSR)] are equilibrated in solution through an intermediate enolic form.
S S R RThe more stable (C S ; C S ) diastereomer pair is strongly stabilised by Oδ-
(CO).....Sδ+(SO) charge transfer and electrostatic interaction and the less
stable (CRSS; CSSR) diastereomer pair is stabilised into a lesser extent by means of Oδ-
(SO).....Cδ+(CO) and Oδ-
(CO).....Sδ+(SO) interactions. The
Hδ+CH3S(O).....Oδ-
(CO) and Hδ+CH3S(O).....Oδ-
(POEt) hydrogen bonds are also responsible for the stabilisation of both diastereomer pairs. The X-ray diffraction analysis of the meta-(Ia) derivative shows that it is stabilised in the more polar (CRSS; CSS
(SO)l h o
[FAPESP, CNPq]
R) diastereomer pair whose conformation is slightly distorted relative to that found in gas phase. The Oδ-
....Cδ+(CO) , Oδ-
(POEt)....Cδ+(CO), Oδ-
(CO)....Pδ+P(O)
and Hδ+CH3S(O).....Oδ-
(POEt) intramo ecular interactions stabilise t is conf rmation in the solid state.
110
P13-Mo
REGIOCHEMISTRY OF NUCLEOPHILIC ATTACK OF CYCLIC SULFATES
Tony K. M. Shing* Vincent W.-F. Tai and Leong H. Wan
Department of Chemistry, The Chinese University of Hong Kong, Shatin,
Hong Kong, China *[email protected] Cyclic sulfates, in synthetic view point, are more or less the same as epoxides. They can be opened by nucleophiles to give an alcohol after acid hydrolysis.1 If the epoxide or the cyclic sulfate is located within a six-membered ring, the regioselectivities of their ring openings are different. For epoxides, nucleophilic attacks leading to diaxial products are much more favored.2 For cyclic sulfates, on the basis of our work,3-6 there are two major factors that govern the regioselectivity of charged nucleophilic openings, namely stereoelectronic factor2 (alignment of dipoles)7 and steric factor3-6 (conformation of the substrate and the size of the nucleophile). A comparsion with that of cyclic sulfites will also be made.
OBnOBnBnO 5
major product
OBnOBnBnO
(i)
Nu
OH
1 2
OS
O
OO
1. Nu-
2. H3O+, THF
Nu- = I-, PhSe-, AcO-, N3-
(ii)
References
(1) Kolb, H. C.; Van Nieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483.
(2) Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry; Pergamon Press: Oxford, 1983.
(3) Shing, T. K. M.; Tai, V. W.-F. J. Org. Chem. 1995, 60, 5332. (4) Shing, T. K. M.; Tai, V. W.-F. J. Chem. Soc., Perkin Trans. 1 1994,
2017. (5) Shing, T. K. M.; Wan, L. H. Angew. Chem., Int. Ed. Engl. 1995,
34, 1643. (6) Shing, T. K. M.; Wan, L. H. J. Org. Chem. 1996, 61, 8468. (7) Buchanan, J. G. In MTP International Review of Science, Organic
Chemistry Series One; Aspinall, A. O., Ed.; University Park Press: U.S.A., 1973; Vol. 7, p. 33.
111
P14-Mo
THE ROLE OF ALKYLTHIO SUBSTITUENTS ON TETRATHIAFULVALENE AND 1,3-DITHIOLE RINGS.
A THEORETICAL STUDY.
Raquel Andreu, Javier Garín and Jesús Orduna
.
Departamento de Química O e Ciencia de Materiales de Universidad de Zaragoza-CSIC.
rgánica. Instituto d
Aragón.
Alkylthio substituents commonly considered as donor groups cause
increased oxidation potentials when attached to tetrathiafulvalenes and are consequently regarded as electron withdrawing groups relative to this strong donor. However, the recent discovery of tetrathiafulvalene derived donor-acceptor molecules with second order nonlinear optical activity1 questions that assumption since the introduction of alkylthio groups renders tetrathiafulvalene a better donor and increases the nonlinear optical activity of these molecules.
NC CN
S
S
S
S
NC CN
S
S
S
SS
SE1= 0.54V; E2= 0.84Vµβ(0) = 470 10-48 esu
33 nm
E1= 0.59V; E2= 0.90Vµβ(0) = 560 10-48 esu
λmax = 612 nm λmax = 6 In alkylthio groups on these processes we alkylthio donors and the unexpectedly high oxid n g the non r
order to clarify the effect of have performed DFT calculations. The results obtained reveal that
groups behave as weak electron atio potentials are mainly due to solvent effects. Concernin
linea optical behaviour, the contribution of the n→π∗
lowest en sorption is responsible for the increased hyperpolarizability. [1] zJ.; A á2001, 66,
transition to the ergy ab
Gon ález, M.; Segura, J. L.; Seoane, C.; Martín, M.; Garín, J.; Orduna, lcal , R.; Villacampa, B.; Hernández, V.; López, J. T. J. Org. Chem.
8872.
112
P15-Mo
STRUCTURES OF 1-(ARYLTHIO)NAPHTHALENTHER WITH THE SELENIUM AND OXYGEN DERIVAT
ES, TOGE IVES
IONS
W
IN CRYSTALS AND SOLUT
arô Nakanishi, Satoko Hayashi and Takahito Nakai Department of Chemistry, Faculty of Systems Engineering,
As nonbonded G---Z interactions are developed, modeled by 8-G-1-(p-YC H
1 – 3 in solutions are also investigated based on the NMR data: δ(H-2) and δ(H-8) are plotted versus δ(C-i), which are analysed as two correlations for each. Details will be discussed in the presentation.
Wakayama University, 930 Sakaedani, Wakayama 640-8510 (JAPAN) [email protected]
6 4Z)C10H6 (Z = S, Se, O),1 it becomes inevitable to establish the basic structures without influence of nonbonded interactions.
Structures are determined for non-oily compounds in 1-(p-YC6H4Z)C10H7 (1 (Z = S), 2 (Z = Se)2 and 3 (Z = O): Y = H (a), OMe (b), Me (c), Cl (d), Br (e), COOEt (f) and NO2 (g)) by the X-ray crystallographic analysis. Figure 1 shows the structures of 1b and 1e, together with the proposed interactions. They are type B and type A, respectively.
Structures of
S
OMe Cl COOEt
Y
H Z Y
H8Z
H2OSe
H Me Br NO2
res of 1b and 1e, together with the proposed interactions.
f g
A
21 3Z =
a b c d e
Y =
Y
H
Type B ; Interaction of np(Z) π*(Nap)
1e
Z
1b
Fig. 1 The structu
Type ; Interaction of np(Z) π*(Ph)
[1] W. Nakanishi et al., J. Am. Chem. Soc. 1998, 120, 3635-3640; J. Org. Chem. 2002, 67, 38-48; J. Org. Chem. 1998, 63, 8970-8800; J. Org. Chem. 1999, 64, 6688-6696.
[2] W. Nakanishi et al., Euro. J. Org. Chem. 2001, 3933-3943.
113
P16-Mo
S
M. Vorona, J. Melnik, G. Veinberg, S. Belyakov and E. Lukevics
YNTHESIS AND STRUCTURAL ANALYSIS OF STEREOISOMERIC 7-ALKYLIDENECEPHALOSPORANATES
Latvian I 1006, La
Intensive SAR investigations of 7-alkylidenecephalosporanates, their esters,
nstitute of Organic Synthesis, 21 Aizkraukles Street, Riga, LV tvia, [email protected]
sulfoxides and sulfones during the last decade resulted in the discovery of numerous compounds with potent antibacterial, antiinflammatory and anticancer activities [1].
In this communication we present the synthesis of stereoisomericcephalosporanates 3-5 and their structural analysis based on 1H NMR spectra and X-ray crystallographic studies of tert-butyl 7[(Z)-acetylmethylene]-cephalosporanate sulfoxide (4a) and sulfone (5a).
Target compounds 3-5 were obtained condensing tert-butyl 7-oxocephalosporanate (1) and appropriate phosphoranes 2.
SO R1CH=PPh3 S
R1
HH H S
H
R1H
CH2RCOOBu-t
O CH2RCOOBu-t
O
1 R=H, R=OAc
2
3a,b 7Z-isomer
CH2RCOOBu-t
O
3a,b 7E-isomer
+
MCPBA
S
CH2RCOOBu-t
O
R1
HH
4a,b 1S-isomer
S
CH2RCOOBu-t
O
R1
HH
4a,b 1R-isomer
+MCPBA
O OS
CH2RCOOBu-t
O
R1
HH
5a,b
O
a R=H, R1=MeCO; b R=OAc, R1=Me3SiC CH.
O
Unambiguous stereochemical determination of 1S and 7C atoms in 4a and 5a created prerequisites for structural identification of isomeric couples 3b and 4b on the base of chemical shifts of protons attached to C-2, C-6 and C-9 atoms of cephalosporine skeleton. [1] G. Veinberg , M. Vorona, I. Shestakova, I. Kanepe, E. Lukevics, Cur.
Med. Chem., 2003, 10, 1741-1757.
114
P17-Mo
STUDY S
OF THE COMPLEXATION OF HETEROCYCLIC COMPOUNDS DERIVED OF THE BENZIMIDAZOLE.
R.ZNIBER, A.MOUSSAÏF, R.ACHOUR, M.EL GHOUL. Université Mohammed V-Agdal, Faculté des Sciences,
.Ibn Batouta, B.P.1014, Rabat, MAROC.
ize of the cavity, the number and the
l to the dimension of the cavity.
s. Various methods were reported by the literature such as the
potentiometrie, the nuclear magnetic resonance and the spectrophotometrie UV.
In the present work, we studied the photophysics properties of compound A
Laboratoire de Chimie Organique Hétérocyclique, Av
It was noticed that any access to a new class of macrocyclic
compounds is accompanied with a study of their complexantes properties.
These last ones are influenced by the s nature of the present heteroatomes in the macrocycle as the nature of
the used cation. On the other hand, the macrocycles which contain heteroatomes on base of ethers crowns are the excellent ligands for the ions metal, in particular when the ionic ray is identica
They can be used as carriers of metals through membranes, selective extractors of ions as well as the other ecological application
as well as the influence of the complexation of metals transition on the fluorescence.
N
N S
N
H S
N
N
N
H A
The main characteristic of the compound A is the presence of the nitrogen and sulfur atoms instead of those of nitrogen and oxygen,
mbin
ansition metals / ligand A
co ation present in most of the macrocycles.
This substitution of the oxygen atom by the sulfur has an effect on the forming constants of the complexes of trcorresponding.
115
P18-Mo
THE SYNTHESIZED OF HIGH CONJUGATED 3,4-DISUBSTITUED
Istanbul Technical University, Faculty of science and letters De ul
of terest in research fields as diverse as natural product synthesis, drug
design,
ne-containing compounds. Given
ected that most of these synthetic thiophene derivatives have been prepare
, Suzuki and Heck couplings have been reported in the literature. By contrast, there are only a few reports on the synthesis of 3,4-disubstituted thiophene and derivatives in metal-catalysed cross-coupling reactions.
THIOPHENE COMPOUNDS
Okan Sirkecioğlu, Suzan Mutlu
partment of chemistry, 80626, Maslak, Istanb
The preparation of polyfunctionalized heterocyclic compounds is one in
molecular recognition and materials science, In this regards, thiophene-based compounds are considered an important class of materials which show intrinsic electronic properties such as luminescence, redox activity and electron-transport. Over the past few years, the isolation of naturally occuring thiophene derivatives has stimulated much interest as a consequence of their wide range of photobiological activities. This has led in turn to the biologically-guided synthesis of novel thiophe
the ready availability of halogenated thiophenes and the current development of metal-catalyzed cross-coupling chemistry, it is not unexp
d by applying transition metal-catalyzed carbon-carbon bond-forming reactions representative examples of the use of the Tamao-Kumada-Corriu, Negishi, Sonogashira
S [1] H. Frohlich, W.Kalt, J. Org. Chem. 1990, 55, 2993-2995. [2] A. K. Mohanakrishnan, M. V. Lakshmikantham, Carol McDougal, Michael P. Cava, Jeffrey W. Baldwin, and Robert M. Metzger J. Org. Chem. 1998, 63, 3105-3112
N N
SS
116
P19-Mo
PHOTOCHEMICAL REACTIONS OF BENZO[b]THIOPHENE-2,3-DIONES WITH 2,3-DIMETHYLBUT-2-ENE
J
iro Tatsugi and Naoki Shimazaki
Department of Applied Chemistry, Faculty of Engineering, Aichi Institute of Technology, Yachigusa, Yakusa-cho, Toyota 470-0392 (JAPAN)
of photocycloaddition products 2 and 3 can be explained in
In the course of our studies on photochemical behaviour of
cyclic vicinal polycarbonyls1 we have investigated the photochemical reactions of benzo[b]thiophene-2,3-diones with alkenes.
In this communication, we describe the photochemical reactions of benzo[b]thiophene-2,3-diones (1) with 2,3-dimethylbut-2-ene in degassed benzene solution underwent [4 + 2] cycloaddtion to give dioxene derivatives (2) in excellent yields. In the case of these reactions in acetone solution afforded 2 as a major product together with oxetane derivatives (3). The ratio of formation terms of the contribution to its ability to stabilise resonance structures to the reaction intermediates.
[1] J. Tatsugi, K. Ikuma, Y. Izawa, Heterocycles, 1996,43, 7; J. 6, 8611; J. Tatsugi, K. Ikuma, Y. Izawa, Tetrahedron Lett., 1995, 3
Tatsugi, T. Hara, Y. Izawa, Chem. Lett.,1997,177.
117
P20-Mo
DIFFERENT BEHAVIOUR OF THIOPHENE DERIVATIVES IN COMPARATIVE HYDROSILYLATION REACTIONS OF
HETEROARYL AND ARYL AZOMETHINES
Edmunds Lukevics, Irina Iovel, Lena Golomba
Latvian Institute of Organic Synthesis, 21 Aizkraukles Street, Riga LV-1006, Latvia
In the course of our previous investigations1,2 the addition of triethylsilane to the CH=N bond of the thiophene and aromatic Schiff’s bases was studied in the presence of Pd(I) and Rh(I) complexes. The hydrosilylation of the aromatic aldimines leads to the formation of the normal products – N-silyl amines (1) and corresponding amines (2). Unexpectedly, the hydrosilylation of the thiophene imines containing bulky CF3 or Br functional groups in ortho-position of the aza-part of the molecules gave in the addition to the compounds 1 and 2 also the unusual products – C-silyl amines (3).
The proposed mechanism of the N- and C-silylation of the zomethines catalyzed by Pd(I) and Rh(I) complexes will be discussed.
[1 . 2
] I. Iovel, L. Golomba, J. Popelis, S. Grinberga, E. Lukevics Chem. eterocyclic Comps. 2003, 39, 49.
a
] I. Iovel, L. Golomba, J. Popelis, E. Lukevics Chem. Heterocyclic Comps002, 38, 46.
[2H
118
P21-Mo
R
Lyudmila G. Shagun, Mikhail G. Voronkov, Svetlana V. Amosova
EACTION OF 1-HALOGEN-2-ORGANYLETHANE-2-THIONES WITH THIOLS
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,1, Favorsky Street, Irkutsk, 664033,
E-mail: voronkov@ irioch.irk.ru
1-Ha
logen-2-organylethane-2-thiones are distinguished by high and
specific reactivity in the processes of nucleophilic addition and substitution. The interaction of equimolar amounts of propanethiol or trhiophenol with 1-halo-2-organylethane-2-thiones 1 has been found to form 1-halo-2-(organylthio)propane-2-thiols 2 in 73 % yield. With two-fold excess of the thiones 1 under analogous conditions 1-(organylthio)ethane-2-thiols 3 are obtained in 84 % yield. The introduction of 1,2-ethane-dithiol leads to 2-methyl-1,4-dithiane-2-thiol 4 in 81 % yield.
S
Hal
S
S
SH
HS
SH
HS
OHS
SHHal
HS
NH2
RSH
NH2
Hal-
+
SH
S
SHHal
OH
SR
RSHSHSR
SR
R = Me, Ph; Hal = Cl, Br
Hal
1
2
43
56
The heterocycle 4 results from nucleophilic addition of the thiol to the thiocarbonyl group and subsequent intramolecular cyclization with liberation
f hydr
his affords 4-(chloromethyl)-3-thiapentan-1-ol-4-thiol 5. The addition to 1
hydrohalide 6. NMR
o ogen halide. The reaction of 1 with 1,2-hydroxyethanethiol mainly involves the nucleophilic addition of the thiol group to the thiocarbonyl one. Tof 1,2-aminoethanethiol occurs in the same manner to form the corresponding The structure of compounds 2-6 was proven by IR and (1H, 13C)spectroscopy.
119
P22-Mo
VINYLTHIYLATION OF OCTAFLUOROTOLUENE AND ITS DERIVATIVES
Svetlana V. Amosova, Galina M. Gavrilova
A. E. Favorsky Irkutsk Institute of Chemistry SB RAS
[email protected] 1 Favorsky Str., Irkutsk 664033 (RUSSIA)
Earlier, using the reaction of hexafluorobenzene with ethenethiolate
expected 1,3,6-tri(vinylthio)-4-ifluoromethyl-2,5-difluorobenzene (2) (13%).
anion, readily generated from divinylsulfide under the action of sodium in liquid ammonia, we synthesized in preparative yield di- andtetra(vinylthio)fluorobenzenes, reactive monomers and intermediates for fine organic synthesis.1 Interaction of octafluorotoluene (1) with a three-fold excess of ethenethiolate anion at 10-20°C in DMF (instead of liquid ammonia, in which ethenethiolate anions are commonly prepared) unexpectedly gave 1-dimethylamino-2,5-di(vinylthio)-4-trifluoromethyl-3,6-difluorobenzene (3) in 73% yield, along withtr
CF3
F
F
F
F
F
1
DMF
S
CF3
S
F
F
S
F
2
+
CF3
S
F
N(CH3)2
S
F
3 This compound is formed as a result of transamidation of
octafluorotoluene with dimethylformamide. The reaction of 1-amino-4-trifluoromethyl-2,3,5,6-tetrafluorobenzene (4) with ethenethiolate anion in DMF at 10-20°C afforded 1-amino-2,5-di(vinylthio)-4-trifluoromethyl-3,6-difluorobenzene (5) in 18% yield.
5
F
NH2
S
4
F
NH2
F
Thus, it has been shown that when perfluorobenzene contains an electron-withdrawing substituent (CF3), solvents (NH3 liq. and DMF) also act as reagents offering a strong competition to ethenethiolate anion in nucleophilic substitution reactions. The data obtained allow the targeted synthesis of polyfunctional per
CF3
SFS
DMF
CF3
FF
fluorobenzenes.
ova, V. I. Gostevskaya, G. M. Gavrilova, A. V. Afonin, L. S. omanenko and L. Stefanik Zh. Org. Khim. 1992, 28, 1463-1466.
[1] S. V. AmosR
120
P23-Mo
UN 5-TETRAFLUOROBEN OSEMICARBAZIDE
EXPECTED REACTION OF 3,6-BIS(VINYLSULFONYL)-1,2,4,ZENE WITH THI
Svetlana V. Amosova, Galina M. Gavrilova
A. E. Favorsky Irkutsk Institute of Chemistry SB RAS 1 Favorsky Str., Irkutsk 664033 (RUSSIA)
s to obtain the heterocycle 3 from the diadduct 2 in DMF at 75-80°C in 81% yield, along with a 18% yield of the heterocycle 4.
3,6-Bis(vinylsulfonyl)-1,2,4,5-tetrafluorobenzene (1) represents a convenient system for assembling diverse heterocycles through nucleophilic addition and substitution reactions.1,2
We have found that reacting vinylsulfonylfluorobenzene 1 with thiosemicarbazide (1:2 ratio) in ethanol or DMF (20°C) gives 3,6-bis(2-thiosemicarbazidoethylsulfonyl)-1,2,4,5-tetrafluorobenzene (2) in 73% yield. Unexpectedly, increasing the reaction temperature to 75-80°C in DMF and using a four-fold excess of thiosemicarbazide afforded the fluorinated nitrogen- and sulfur-containing condensed heterocycle 3 in 54% yield. The use of a stronger base, tributylamine, allowed u
SO2
F
FSO2
F
F
1
NH2NHCNH2
SSO2
F
FF
F
NHNHCNH2
S
(C4H9)3N
O2SN
N
S
F
F NH2S
+
O2SN
N
S
F
F N 2H
2 SO2
NHNHCNH2
S SO2H2NCNHNH 3 4
The heterocycle 3 is formed as a result of the nucleophilic addition of 1-NH2 group of thiosemicarbazide to double bonds of vinylsulfonylfluorobenzene 1 followed by intramolecular substitution of fluorine atoms in o- and m- positions of the benzene ring by the NH group and the second nucleophilic center, sulfur atom, respectively.
Structures of compounds 2-4 were confirmed by IR and NMR (1H, 13C, 19F, 15N) spectroscopy. [1] S. V. Amosova, V. I. Gostevskaya, G. M. Gavrilova, V. N. Nesterov and Yu. T. Struchkov Izv. AN. Ser. Khim. 1996, 430-433. [2] S. V. Amosova, V. I. Gostevskaya, G. M. Gavrilova, V. N. Nesterov, Yu. T. Struchkov and L. N. Il’icheva Khim. Geterotsikl. Soed. 1996, 1195-1198.
121
P24-Mo
HIGHLY DIASTEREOSELECTIVE DEUTERATION OF 2-p-LYLSULFINYL ETHYLBENZENE AT BENZYLIC POSITIOTO N
José L. García Ruano, and M. Teresa Aranda
Departamento de Química Orgánica
different electrophiles.1 In this commu
. Universidad Autónoma de Madrid. Cantoblanco, 28049-Madrid (SPAIN)
The sulfinyl group has shown high efficiency for controlling the stereoselectivity in the reactions of the benzylic anion derived from 2-p-tolylsulfinyl ethylbenzene 1 with
nication we describe the stereochemical behaviour of benzylic anion under deuteration conditions, as well as the synthesis of the two possible monodeuteratated diastereoisomers.
S
Me
Tol
HRHS
O
LDA
S
Me
Tol
DR
DS
O
LDA1
1) LDA+
1) LDA+
D+
Ar
Me HR
DS
Ar
MeHS
Ar
Me HR
H+
Ar
Me DR
HS
Ar
MeDS
Ar
Me DR
3a 3b
2
Ar= (S)-2-p-Tolylsulfinylphenyl
2) H 2) D
1) LDA; 2) D+
1) LDA; 2) H+
as 3b yields 1 upon re
rotonation usually takes place with retention of e configuration,2 we can conclude that deprotonation with LDA is highly
ore reacting with the
Sulfoxide 1 was deprotonated with LDA and reacted with CH3OD to afford 3a as only monodeuterated isomer. Monoprotonation of compound 2 under similar conditions produces isomer 3b instead. Monoprotonation of 3a exclusively yields 3b and monodeuteration of 3b only affords 3a. In contrast, reaction of 3a with LDA and CH OD gives 2 where3
action with LDA and CH3OH. By assuming that p
thdiastereoselective but the resulting carbanions are configurationally unstable and they invert their configuration immediately befelectrophile.
122
[1] a) García Ruano, J. L.; Carreño, M. C.; Toledo, M. A.; Aguirre, J. M.; Aranda, M. T.; Fisher, J. Angew. Chem. Int. Ed. 2000, 39, 2736. b) García Ruano, J. L.; Alemán, J.; Soriano, J. F. Org. Lett. 2003, 5, 4513. [2] Stratmann, O.; Kaiser, B.; Fröhlich, R.; Meyer, O.; Hoppe, D. Chem. Eur. J. 2001, 7, 423.
P25-Mo
ASYMMETRIC SYNTHESIS OF CYCLOPROPANES FROM SULFINYLPYRAZOLINES MEDIATED BY ACIDS
José L. Garc rio Martín, ía Ruano, Marina Alonso, Alberto Fraile, Rosa
M. Teresa Peromingo, Amelia Tito.
Departamento de Químic d Autónoma de Madrid. Cantoblanco, 28049-Madrid (SPAIN)
xides (from olefins) and cyclopropanes, are formed in completely stereoselective reactions. The formation of cyclopropanes must be favoured by the presence of acids.2
a Orgánica. Universida
When sulfinylpyrazolines (1) are heated at 100 ºC in toluene, olefins 2 are exclusively obtained.1 The reactions of 1 with MCPBA afford mixtures of cyclopropanes (3) and epoxides (4), the latter being also obtained by oxidation of compounds 2. Remarkably, these processes take place at low temperatures and both products, epo
O
ON
N
OEtRR'
TolOS
O
O
OEt
TolO2S
R
R' O
O
OEt
O
TolO2S
R'R
+2) SiO2, CHCl3, rt
1 3 4
O
O
OEt
TolOS
R'
R 2
Toluene100 ºC
1) MCPBA, CH2Cl2 0 ºC to rt, 4 h.
1,3-Dipolar cycloadditions of 2-p-tolylsulfinyl cyclopentenones (5) with diazoalkanes under different conditions, afford pyrazolines 6. Their catalytic decomposition yields mixtures of cyclopropanes 7 and olefins 8 in a ratio which is influenced by the type and number of equiv of the Lewis acids used as catalysts, the temperature and the stereochemistry of the pyrazolines.
R
OS
Tol
O
CHN2N
N
TolOS
R
OR'
RR=H, MeR'=H, Me
R'
OTolOS
R
OS
Tol
O
R'R'
Lewis acid
5 6 7 8 Mechanistic proposals to account for all the experimental facts, as
well as the synthetic scope of these two highly stereoselective reactions have also been investigated.
[1] García Ruano, J. L.; Fraile, A.; González, G.; Martín, M. R.; Clemente,
Bull.Soc Chim. France 1960, 550.
F. R.; Gordillo, R. J. Org. Chem. 2003, 68, 6522-6534. [2] (a) Doyle, M. P.; Buhro, W. E.; Dellaria Jr, J. F. Tetrahedron Lett. 1979, 4429-4432. (b) Nominé, G.; Bertin, D.
123
P26-Mo
ENA NS
NTIOMERICALLY PURE α−SUBSTITUTED CYANOHYDRIDERIVED FROM BENZALDEHYDE
José L. García Ruano, Ana M. Martín Castro, Francisco Tato, and Diego J. Cárdenas
Departamento de Química Orgánica
Optically pure cyanohydrins are interesting chiral templates. Thus,
their sy
this communication, we report on our results dealing with the hydrocyanation of (S)-2-p-tolylsulfinylbenzaldehyde (1) and its corresponding ketones (2), with Et2AlCN and R3SiCN under different conditions. The stereoselectivity is excellent (de>98%) when reactions are conducted in the presence of some Lewis acids such as Yb(OTf)3 or Y(OTf)3. The observed diastereoselectivity is a consequence of the attack on the most table conformer of a Y(OTf) chelate involving aldehyde and sulfóxide
coordin
, Universidad Autónoma de Madrid, Cantoblanco, 28049-Madrid (SPAIN)
nthesis have been a goal for many authors,1 who have obtained very good results just in case of starting from aldehydes. The sulfinyl group showed a high efficiency to control the stereoselective hydrocyanation on β-ketosulfoxides.2 More recently it has also evidenced its ability to achieve the remote control of the stereoselectivity.3 This has been nicely exploded by Toru in different nucleophilic additions to 2-p-tolylsulfinyl benzaldehyde,4
although its hydrocyanation has never been considered. In
s 3ation as shown by calculation at DFT level.
S Tol
OS Tol
OEt2AlCN or R3SiCN CN
1) Base2) Electrophile
S TolO
CN
H (Me) H (Me)E = CO2R, Alkyl, R-CHNHR'
OOR
(R=H, SiR3)
EOTiPS
We have also studied the reactions of the silylated cyanohydrins derived from aldehydes with bases and different electrophiles. Good results have been obtained with KHMDS and ClCO2Et on the OTIPS derivatives. [1] See
.; Martín Castro, A. M.; Rodríguez J. H. Recent Research Developments in Organic Chemistry 2000, 4(Pt. 1), 261-282.
] Nakamura S.; Masahiro O.; Yasuda H.; Toru, T. Tetrahedron 2001, 57, 8469-8480
, for example: Solis, A.; Luna, H.; Perez, H. I.; Manjarrez, N. Tetrahedron: Asymmetry 2003, 14, 2351-2353. [2] García Ruano, J. L
García Ruano, J. L.; Martín Castro, A. M.; Rodríguez J. H. J. Org. Chem. 1992, 57, 7235. [3] García Ruano, J. L.; Carreño, M. C.; Toledo, M. A.; Aguirre, J. M.; Aranda M. T.; Fischer J. Angew. Chem. Int. Ed. 2000, 39, 2736-2737. [4
124
P27-Mo
EFFICIENT ENANTIOSELECTIVE SYNTHESIS OF ROPANES FROM SULFONYLPYRAZCYCLOP OLINES
José L. García Ruano, Ana M. Martín Castro, and Esther Torrente
Departamento de Química dad Autónoma de Madrid.
Sulfinyl acrylonitriles have shown to be the best monoactivated
vinylsu
Orgánica. UniversiCantoblanco, 28049-Madrid (SPAIN)
lfoxides in asymmetric Diels-Alder reactions,1 and very efficient as chiral dipolarophiles in their reactions with diazoalkanes,2 which afford sulfinylpyrazolines in a completely stereoselective manner in high yields.
In this communication, we describe the use of sulfinylpyrazolines as the starting products to the synthesis of enantiomerically pure cyclopropanes in a short synthetic sequence involving the completely stereoselective extrusion of the nitrogen from sulfonylpyrazolines as the key step.
H
R'R
SO2Tol
CN
H
R'R CN
H
R'R CN
H Mg/MeOHCH2I2/ i-PrMgCl
3 45
LDA/THF -78º
-78º r. t.
NN
H
R'
R
SOTolCN
H
NN
H
R'
R
SO2TolCN
Hm-CPBA
Toluene (∆)
SOTol
CNR'
H
R = H, MeR' = n-Bu, Bn, t-Bu
1 2
NN
R H
Reaction of compounds 1 with m-CPBA afforded sulfones 2. When
they were refluxed in toluene, they evolved into cyclopropanes 3 in alm st quantita
ecessary to complete this reaction successfully. Elimination of the sulfonyl
lic acids derivatives. The
R. ; Rodríguez Ramos, J. H. Org. Lett . 2001, 3, 3173.
otive yields. These reactions take place with a complete retention of
the configuration at all the chiral centres, even in case of the t-butyl derivatives. The presence of both, sulfonyl and cyano groups, seems to bengroup with Mg/MeOH and further transformation of the cyano function provide optically pure cyclopropyl carboxypresence of the SO2Tol moiety in 3 can be used to introduce different electrophiles at the cyclopropyl ring. It can be used in the synthesis of alkylidene cyclopropanes such as 5.
[1] García Ruano, J. L.; Alemparte, C.; Martín Castro, A. M.; Adams, H; Rodríguez Ramos, J. H. J. Org. Chem. 2000, 65, 7938. [2] García Ruano, J. L.; Blanco, D.; Martín Castro, A. M.; Alonso, S. A.; Martín, M. 125
P28-Mo
[7]HELICENEBISQUINONES: ENANTIOSELECTIVE SYNTHESIS BY A DOMINO PROCESS
FROM (SS)-2-(p-TOLYLSULFINYL)-1,4-BENZOQUINONE
M. Carmen Carreño, Marcos González, Antonio Urbano
Química Orgánica. Universidad AutónDepartamento de oma de Madrid. Canto AIN)
their in
eveloped the first asymmetric approach to [5]helicenebisquinones based on the domino Diels-Alder reaction/sulfoxide elimination/oxidation process between enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (3) and vinyl dihidrophenantrenes.2,3 We now report a short and efficient enantioselective synthesis of tetrahydro[7]helicenebisquinones 4 in enantiopure form from sulfinyl quinone (SS)-3 and different bis-dienes 2, in a six-steps one-pot domino process, comprising [4+2]cycloadition, sulfoxide elimination and partial aromatization, which took place twice. Bis-dienes 2 are available in 4 steps using known enone 1 as starting material.
rcía-Cerrada, Antonio Urbano, J. Am. Chem. Soc. 2001, 123, 7929-7930.
blanco, 28049-Madrid (SP
Helicenes are a well-known representative of polycyclic aromatic compounds. These artificial molecules have attracted increasing attention during last years,1 not only by their hitherto physical properties but also by
creasing number of applications in chemistry, both of them closely linked to their enantiopurity.
Despite the remarkable advances in the field, a general, short and stereoselective approach is currently needed. We have recently d
[1] Antonio Urbano, Angew. Chem., Int. Ed. 2003, 42, 3986-3989. [2] M. Carmen Carreño, Susana García-Cerrada, Antonio Urbano, Chem. Eur. J. 2003, 9, 4118-4131. [3] M. Carmen Carreño, Susana Ga
O
O
OO
R
R
O
O
S
p-Tol
O
R = H (96% ee) R = OEt (96% ee)R = OTBDMS (>99.5% ee)
4
1
Tetrahidro[7]helicenebisquinones
2
(SS)-3
(SS)-3
MeO
O OTf
TfO R
R
R = HR = OEtR = OTB SDM
126
P29-Mo
DIASTEREOSELECTIVE ACCESS TO 1,3 SYN-DIOLS BY
Yasm
CONDENSATION OF β-HYDROXYSULFOXIDES/SULFONES WITH ALDEHYDES
in Brinkmannª, M. Carmen Carreñoª, Françoise Colobertb, Guy
ªDepartamento de ma, Cantoblanco,
bLaboratoire de Stéréochimie, UMR 7008 du CNRS, Université Louis Paste
Solladiéb, Antonio Urbanoª Química Orgánica, Universidad Autóno
28049 Madrid, Spain
ur (Ecole Européenne de Chimie, Polymères et Matériaux), 25, rue Becquerel, 67087 Strasbourg cedex 2, France
The stereoselective synthesis of 1,3 syn-diols is of great interest
because they are a common pattern in many natural products. Although sulfoxides are efficient chiral inductors in a wide range of reactions1 their use in condensations is limited due to low asymmetric inductions achieved.
Here we report the obtention of 1,3 syn-diols from enantiopure β-hydroxy sulfoxides/sulfones. The β-hydroxy sulfoxides 1 are easily accessible through the diastereoselective reduction of β-ketosulfoxides2. We describe the results of a study of condensations of β-hydroxy sulfoxides 1 and the corresponding sulfones 2 with several aldehydes.
OS
R
OH O OHDIBALH m-CP
OHO O
Sp-Tol
(O)n
n = 1 and n= 2 p-Tol
OHO O
S
LDA, RCHO
-78 °C, THFR
OH
(O)n
OS
O
Rp-Tol
OS
Rp-Tol
OH
p-Tol
OS
R
OH
Op-Tol
SR
Op-Tol
1
1
2
2
p-Tol
O O
S
R
(O)n
OOMeO OMe
CSA, rt
DIBALH ZnBr2
BA
m-CPBA
high de n = 1 and n= 2 n = 1 and n= 2
Thus, the sulfinyl/sulfonyl anions, after base treatment, were allowed to react with different aldehydes to provide the corresponding syn-diols with high
iastereoisomeric excesses. The configuration of the resulting diols was 3.
v. 1995, 95, 1717-1760.
. Solladié, J. Org. Chem. 1990, 55, 2120-2128. [3] S. D. Rychnovsky, B. Rogers, G. Yang, J. Org. Chem. 1993, 58, 3511-3515.
ddemonstrated through the formation of the corresponding acetonides [1] M. C. Carreño, Chem. Re[2] M. C. Carreño, J. L. Garcia Ruano, A. Martín, C. Pedregal, J. H. Rodríguez, A. Rubio, J. Sánchez, G
127
P30-Mo
ASYMMETRIC CONJUGATE ADDITION OF CHIRALLY
SULFINYLATED 1-INDOLYL ENONES BY A DIARYLCUPRATE
Yoshitsugu Arai,* Makoto Kasai, Yukio Masaki
Gifu Pharmaceutical U gashi, Gifu 502-8585,
tolylsulfinyl)p othly to give the adduct with high diastereoselectivity.1)
As an extension of work, we of chiral 3- and 2-
niversity, 5-6-1 Mitahora-hi
Japan [email protected]
We have recently reported that the conjugate addition of 2-(p-
yrrolyl α,β-unsaturated enones proceeds smo
this were intrigued by the usesulfinyl indolyl enones 1 and 2 for conjugate addition reactions. In
contrast to the pyrrole sulfoxide,1) steric interactions between the H-7 of the indole ring and the N-substituent (= the enoyl group) of 1 and 2 may influence the conformational flexibility of the transition structure.
a4
O O O
tatd
1
di-o-l, p-Tol) as the major
to produce 5b in favour to 6b.
., Ueda K., Xie J., Masaki Y., Chem. Pharm. Bull. 49, 1609—1614 (2001).
Although the diastereoselectivities of the addition of 1 by an rylcopper reagent (Ar2Cu•MgBr•MgBrI) were poor (major products: 4, —34% de’s), with the cinnamoyl derivative 2a, addition reaction of
4a: R = Ph4b: R = Me
5a: R = Ph5b: R = Me
6a: R = Ph6b: R = Me
O RR
1a: R = Ph1b: R = Me
2a: R = Ph2b: R = Me
HN
O RR1
N
O R
SO
p-Tol
R1
N
O R
S
O
p-Tol
R1
N
O R
S
O
p-Tol
R1
3a: R = Ph3b: R = Me
N
S p-Tol
N
O
S p-Tol
H77
32
S p-Tol
olyl- and di-p-tolylcuprates to 2a gave 5a (R1= o-Todducts with high diastereoselectivities (84—86% de’s). The reaction of he crotonoyl derivative 2b also gave high diastereoselectivities (81—88% e’s)
) Arai Y
128
P31-Mo
STEREOSELECTIVE SYNTHESIS OF 1,4-OXATHIANE S-OXIDES
Richard S. Grainger
, Patrizia Tisselli and Simon T. Bedford
Department of Chemistry, King’s College London,
In the course of our recent studies on diastereotopic group selective intra op an the cyclohexadiene system. The o
Strand,London WC2R 2LS (UK)
molecular cycloaddition reactions of sulfenic acids to 1,4-dienes,1 webserved that in the case of an allyl protected alcohol, cyclisation occurs referentially on the allylic alkene rather th
two diastereomeric 1,4-oxathiane S-oxides produced have sulfinyl xygen and adjacent methyl group cis on the 6-membered ring.2
S
Oxylene, reflux
OHOS
O
S
O
S
O
O O SO
OH
SO
O H
35%55%
++
This poster will describe our studies into the generality of this new method for generating 1,4-oxathianes, and its application in target synthesis. [1] G1[ . P
rainger, R. S.; Tisselli, P.; Steed, J. W. Org. Biomol. Chem. 2004, 2, 51. 2] Jones, D. N.; Hill, D. R.; Lewton, D. A.; Sheppard, C. J. Chem. Socerkin Trans. 1, 1977, 1574.
129
P32-Mo
A CONVENIENT SYNTHESIS OF THIOACETATES AND THIOBENZOATES USING SILICA-GEL SUPPORTED POTASSIUM
Tad
THIOACETATE AND THIOBENZOATE
ashi Aoyama,1,* Toshio Takido,1 and Mitsuo Kodomari2
1Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University; Kanda Surugadai, Chiyoda-ku, Tokyo 101-
ed for the synthesis of thioesters by a reaction of alkyl halides with silica-gel supported potassium thioacetate or thiobenzoate under mild conditions.
Recently, many reactions using supported reagents have been
reported. We have found that potassium thioacetate can be activated remarkably by supporting onto silica-gel, and silica-gel supported potassium thioacetate (AcSK/SiO2) reacts with alkyl halides in nonpolar solvents such as benzene to give alkyl thioacetates in good yields. In this communication, we describe a convenient procedure for the conversion of alkyl halides 1 into alkyl thioacetate 2 by using AcSK/SiO2.
8308, Japan 2Department of Applied Chemistry, Shibaura Institute of Technology;
Shibaura, Minato-ku, Tokyo 108-8548, Japan [email protected]
A simple and efficient procedure has been develop
XR'COSK / SiO2R R'COS RX = Cl, Br, IR' = Me, Ph
1 2
Benzyl bromide did not react with finely ground potassium
ioacetate suspended in benzene at room temperature. In contrast, similar
mong the inorganic supports tested. Alumina was also effective but less
morillonite K10 were ineffective for activating potassium thioacetate.
ding thioacetates in high yields. Substituted enzyl halides were converted into the corresponding thioacetates in
excellent yields at room temperature. For instance, 4-methyl and 4-nitrobenzyl bromide were converted into the corresponding thioacetates in 98% and 97% yields. Xylylene dibromides produced only disubstituted compound. Mono substituted compound were not detected.
threaction with AcSK/SiO2 proceeded easily under similar conditions to afford benzyl thioacetate in 83% yield after 1h. Silica-gel was the most effectiveathan silica-gel. Molecular sieves 4A was much less effective. Celite and Mont
The reaction of a series of organic halides with AcSK/SiO2 in benzene gave the corresponb
130
P33-Mo
NOV NS
Kurt Wermann
EL HETEROCYCLIC IMIDOTHIOATE ZWITTERIOAS INTERMEDIATE IN RING TRANSFORMATIONS
, Martin W lther, and Ernst Anders
In
a
stitut für Organische Chemie und Makromolekulare Chemie der Friedrich-Schiller-Universität, Lessingstrasse 8, D-07743 Jena, Germany
E-Mail: [email protected] We S“ heterocycles 1 ines 2 which proceed under retentproduct
3a
Our discussion of the mechanism of these ring opening and ring closure reactions consider the fact that the novel imidothioate intermediates 3 can
e isolated and detected via their characteristic NMR signals and X-ray alysis
[4] K. W
report on interesting ring transformations of our novel „5/6/5-NNafter ary amreaction with primary or second
ion or loss of sulfur. The formation of the reaction s 4 (oligo substituted guanidines bearing up to three heterocyclic
moeties) and 5 (novel „5/6/5-NNN“ heterocycles) proceed via multi-step cascade reactions in which, after the initial amine attack at the C atom, specific bond breaking and bond forming processes occur.
N
N
NN
N S
N
R1
R2R2
I
R3
" 5/6/5-NNS" heterocycles
HNR4
H(R5)+
2
1
N
N
NN
N S
N
R1
R2
R2
R3N
R4 R5 R1I
NN
NR2
R3N (E) N
NR4 H(R5)
S
N (Z)
R1
R2
3
4and/or
" 5/6/5-NNN" heterocycles
N
N
NN
N N
NR2R2
R3 R4
5
ban . High-level DFT calculations explain the reaction pathway which lead to 4 and/or 5. [1] K. Wermann, M. Walther, W. Guenther, H. Goerls, and E. Anders, J. Org. Chem. 2001, 66, 720 - 726. [2] M. Walther, K. Wermann, H. Goerls, E. Anders, Synthesis 2001,1327 – 1330. [3] K. Wermann, M. Walther, E. Anders, ARCIVOC 2002 (X) 24 – 33.
ermann, M. Walther, W. Guenther, H.Goerls, E. Anders, Eur. J. Org. Chem. 2003, 1389 – 1403 [5] K. Wermann, M. Walther, W. Guenther, H.Goerls, E. Anders, Synlett 2003, 1459 – 1462. [6] S.O. Nilsson Lill, G. Rauhut, E. Anders, Chem. Eur. J. 2003, 3143-3153.
131
P34-Mo
SOME NOVEL HETEROCYCLIC COMPOUNDS FROM POLYHALOBUTADIENES
Cemil İBİŞ and Nihal YILMAZ
Istanbul University, Faculty of Engineering, Department of Chemistry,
Avcılar, Istanbul [email protected]
It is known that some heterocyclic compounds have got biologic
thioethers. These resulting products are formed by additions-eliminations reactions mechanism.
The novel compounds are purified by column chromatography. These compounda are characterized by elemental analyses and spectroscopic methods, such as IR, MS, NMR.
,Chem. Ber. 1981, 114, 682. 2,
[4] İbiş, C., und sayıl Ç. Synth.Commun., 1994, 118, 49. [5] İbiş, C., Göksel F. S., Sayıl Ç. Phosphorus, Sulfur, and Silicon, 1995, 107, 227.
activites (herbicides, insectisides...etc)1. In addition, polyhalogened butadienes are very reactive compounds. These compounds react quickly with thiols and dithiols.
In our previous studies we have reported that thiosubstituted butadienes were obtained from the reactions of polyhalobutadienes with dithiols2-5. Our studies on this subject are continued.
The reactions of polyhalobutadiene and thiols gave
S
Cl
S
ClCl
R'
S
Cl
Cl
Cl
ClS
Cl
Cl Cl
Cl
ClR'
Cl
Cl
S
ClCl
ClS R'
S
Cl
ClCl
ClS
ClCl
ClR'
Cl ClCl Cl
SO
ClCl
SCl R2
(CH ) (CH ) (CH ) O (CH ) O CHR' = ...e,2 4 2 5 2 2 2 2 2 tc.,S
CH2 CH CH2...etc.R2 =
[1] Roedig A., İbiş C., and Zaby G.[2] İbiş C., Gökmen Z., Yılmaz.N., Phosphorus Sulfur and Silicon. 200177, 2907. [3] İbiş, C., Bull. Soc. Chim. Belg., 1996,105, 317.
132
P35-Mo
NOVEL CYCLIC AND ACYCLIC SULFUR COMPOUNDS FROM p-CHLORANIL
F. Serpil Göksel, Cemil Ibiş and Nilüfer Akgün
Istanbul University, Engineering Faculty, Department of Chemistry, Av ey
cılar 34320, stanbul,TurkI
In recent years, a growing interest has emerged in new chloranil derivatives because of their possible biological activity and concerning superconductivity.The superiorconductivity is mainly attributable to interm
ty of new thioquinones having mono or dithio groups were
The products were purified by chromatography and subsequently recrystallized, structures of the compounds were determined by spectral data.
olecular sulfur-sulfur interactions of the fused ethylene dithio groups in the crystal structures .1,2
A varieproduced with p-chloranil.
CH2OH S (CH2)6 CH3
S SO
SS O
O
O
Cl
ClS
S
O
O
O
S
S
O
O
O
OH
S
S
SCH2
O
O
SCl (CH2)6 CH3
) -CH
R
R
R
; , etc ...(CHR : 2 3 3
[1] Otsubo,T., Nobuhara,Y., Kanefuji, Aso,Y.; Ogura,F., J. Phys. Org.
,S.; Harlev,E.; Synthesis 1989, II, 868-869.
Chem. 1988, 5, 1,275 – 280. [2] Bittner
133
P36-Mo
SYNTHESES OF BENZIMIDAZOLO [3,2--ONES
Moh
B][2,4]BENZOTHIAZEPINE-10(5H)
ammad Abdollahi, Noushin Rastkari, Abbas Shafiee
Pharmaceutical Sciences Research Center, Tehran University of Medical
Sciences, Tehran 14174, Iran E.mail: [email protected]
he derivatives of benzothiazepines are a class of fused heterocycles of considerable interest owin ty of their biological ctivities such as CNS depresants1, anti HIV2, etc. Among the fused eterocycles systems which have been prepared the Benzimidazolo [3,2-
b][2,4
Tg to the remarkable diversi
ah
] benzothiazepin-10(5H)-ones, is notable by its absence. In this work syntheses of some derivatives of this new heterocyclic system are described. The title compounds ere prepared according to Scheme.3
N
SH +
CH2Cl RN
NH
2
N S
RCOCl
CH3CN (dry)
1 3 Raney Ni R=NO2
4
O
R=H, CH3, NO2
N
S
OH2N
N
1) Bartsch H. et al., studies on the chemistry of O, N-and S, N-containing Heterocycles. 3[1]. Synthesis of 1,5-Benzothiazepines with potential CNS Activity. J. Heterocycl. Chem. (1991), 26. 835-8 2) Grandolini G. et al., Synthesis of some new 1,4-benzothiazine and 1,5-benzothizepine tricyclic derivatives with structural analogy with TIBO and their screening for anti-HIV activity. Eur. J. Med. Chem. 34 (1999) 701-109.
enzothizepin-10(5H)-ones J. Chem. Research (s). (2002) 178-179
3) Bakavoli M. et al., Regioselective synthesis of [1,2,4]triazolo[3,2-b][2,4]b
134
P37-Mo
SYNTHES METRIC
IS OF CHIRAL BIS-THIZOLINES AND ASYMDIELS-ALDER REACTION
Takehiko Nishio, Yasuhiro Kodama# and Yuji Tsurumi# Department of Chemistry and Graduate School of Environmental Sciences,#
University of Tsukuba, Tsukuba-shi, Ibaraki, 305-8571 Japan [email protected]
Novel synthesis of chiral bis-thiazolines by the reaction of chiral bisacylamino) alcohols with Lawesson's reagent (LR) and ability of these neligands to act as chiral catalysts in Deals-Alder reaction are described
HOHN X
HN
OHS
N
X
N
SLR
-(N-w
.
xample, when 3-acryloyloxazolidine-2-one 10 was treated with cyclo-
The reaction mechanism for the formation of bis-thiazolines and cycloadducts will be discussed.
N
R R
S
N N
S
R R
S
N N
S
R R
Z NN
S
N
SS
N
R RR
X; C(Me)2 , CH2CH2,
R: Ph, Bn, i-Pr
5-8
5 6 7: Z =CH8: Z =N
9
R RO O
Treatment of chiral bis-(N-acylamino) alcohols 1 with LR in toluene at reflux temperature yielded chiral bis-thiazolines 5-8 in good yields. Chiral bis-thiazolines 5-8 thus obtained, sulfur analogues of known oxazolines, can be expected to be new chiral ligands for metals in various reactions. For epentadiene 11 in the presence of zinc triflate and bis-thiazoline 6, the cycloadducts were obtained as a 94:6 diastereomers where the major daistereomer, formed with good enantioselectivity (92 % ee).
O N
O O
NH H
+ Chiral CatalystO
O
NOO
O
Lewis acid
10 11O
(S)-endo (R)-endo
(S)-exo (R)-exo
135
P38-Mo
NEW HETEROCYCLIC COMPOUNDS FROM MONO(THIO)SUBSTITUTED NITRODIENES
Cemil IBIS, M.Çigdem SAYIL and Funda ÖZKÖK
anbul University, Engineering Faculty, Department of ChemistIst ry
[email protected],Avcilar/TURKEY
es.In this study, N,S-substituted butadiene compounds have been obtained from these reactions. A number of mono(thio)substituted compounds of 2-nitropercholorobutadienes were also prepared previously1. It is known that some heterocyclic compounds have got biologic activities such as herbicides, insecticides, fungucides etc. from US-patent2. From the spectroscopic data and related literature it can be conculuded that these new compounds are formed by substitution of chlorine atoms bound to the first carbon of nitrodiene with N-nücleophiles. The new compounds are purified by chromatography on silicagel. These compounds are chracterized by micro analysis and spectroscopic methods ( IR, NMR etc ).
[1] Cemil Ibis and Cigdem Sayil Rev. Roum. Chim., 2001, 46 (3), 211-216. [2] Diamond Alkali Company ( Erf. H.Bluestone ), US-Pat. 3021370 (13.Febr. 1962) [ Chem. Abstr. 57, 3293c (1962)].
The aim of this work is to investigate the reaction of the very reactive mono(thio)substituted 2-nitropercholorobutadienes with some piperazin
N NCl
Cl
NO2
CIS-R
FCl
Cl
Cl S-R
NO2
N NN
R= CH3-(CH2)11-, CH3-(CH2)15-... vs
Cl
Cl
Cl S-R
NO2
N N N H
OCIN
Cl
Cl
Cl S-R
NO2
N
SR
NO2
CI
CI
136
P39-Mo
N2S IC IMINOSULFIDES AND ITS APPLICATION AS LIGANDS FOR
COMPLEXATION WITH Ni(II) AND Со(II)
Elena K. Beloglazkina
2-TYPE IMINOTHIOLATE AND MACROCYCL
, Nikolai V.Zyk, Andrei A.Chijevskii, Yuri
M.V.Lomonosov Moscow State University, Chemistry Department, Vorobievy gory, Moscow, Russia, 119992
B.Chudinov, Anna A.Moiseeva, Kim P.Butin
Synthetic approaches to the polydentate N,S-containing ligands and its complexes with Ni(II) and Со(II) with the following structures are worked out:
The template condensation of corresponding carbonyl compounds with appropriate diamines in the presence of metal salts was used for the synthesis of complexes I-II. In the case of complexes III the macrocyclic ligands with different size of spacer between S and N atoms were obtained previously, and then they were put to the complexation reactions.
The synthesized ligands and complexes were characterized by
r two-electron reduction actions that results in formation of a reduced complex, very active in SN2 actions with different alkylating agents.
The authors wish to thank the Russian Foundation of Fundamental Researches (Grant 04-03-32845-а) and the Foundation “Universities of Russia” for a financial support of this work.
elemental analysis, X-rays, NMR, IR, UV-spectroscopy data. All synthesized complexes were investigated by voltammetric
method in the electrochemically activated single- orere
137
P40-Mo
PSEU FOR
Mihail Lucian Birsa
DO-GEMINAL [2.2]-PARACYCLOPHANE AS SPACER BISALLENYL SULFOXIDES AND SULFONES
and Henning Hopf
Institut of Organic Chemistry, Technical University Braunschweig, Hagenring 30, D-38106 Braunschweig (GERMANY)
tropic rearrangements of propargylic sulfenates to
llenic sulfoxides had received extensive application in organic synthesis. This re
aterials for intra- or intermolecular reactions can be synthesized.
We describe here the synthesis of the first pseudo-geminal bisallenyl[2.2]-paracyclophanes by the reaction of the corresponding propargylic alcohols (1) with trichloromethanesulfenyl chloride. A double [2,3]-sigmatropic rearrangement of propargylic sulfenates provides the corresponding bisallenyl sulfoxides (2) as a mixture of four inseparable diastereoisomers.
er. Most likely, the less hindered meso f
ns of the above systems may rovide interesting polycyclic structures.
The [2,3]-sigmaa
action takes place spontaneously at low temperature. On the other hand, using doubly substituted [2.2]-paracyclophanes as spacers for bisallenic moieties, interesting starting m
R
R
OH
OH
R
R
O
O
S
S
CCl3
CCl3
Cl3CSCl 2x[2,3]-σ
SCl3C O
SCl3C O
O
1
RR
SCl C O
RR
SCl C
O
O
O O
2 33
R = C3H7; C4H9; C6H5
3
Oxidation of bisallenyl sulfoxides (2) with dimethyldioxirane leads to the corresponding bisallenyl sulfones (3). These compounds were isolated in moderate to good yields as only one isom
orm, where the trichloromethylsulfone groups point out of the symmetry plane, is formed. The intra- or intermolecular reactio
138p
P41-Mo
NEW SULFUR DERIVATIVES OF ERYTHROMYCIN A: PRELIMINARY STUDIES
Ernesto Brunet, Juan Carlos Rodríguez Ubis, Francisco J. Parra and Susana
Mantecón.
Departam Madrid. Cantoblanc d (SPAIN)
ento de Química Orgánica. Universidad Autónoma de
o, 28049-Madri
O
OOH
O
NHO
HO
HO
6 6
O
OO
O
NHO
HO
HO
NO
OHO
NHO
HO
O
O
O
O
O
OH
O
O
O
O
O
OH
O
O
OHO
O
O
OH
I II III
Erythromycin A (I) is so far one of the most potent, safe exinting antibiotics.2 Some chemical transformations of its structure have yielded other useful semisynthetic antibiotics with better pharmacologic and pharmacokinetic properties such as clarithromycin [II; OMe derivative of Erythromycin A in C(6)] and azithromycin (III; a derivative of Erythromycin A by Beckman rearrangement of the corresponding oxime). There are no reports addressing the introduction of sulphur functions at the aglycon macrolide. Our preliminary results concerning this research will be reported.
[1] Sakakibaro, H.; Omura, S
139
. In Macrolide Antibiotics, Chemistry, Biology, icand Practice; Omura, S., Ed.; Academ : 1984.
P42-Mo
ANTIBACTERIAL AND ANTIFUNGAL ACTIVITY OF SULFUR-CONTAINING COMPOUNDS FROM PETIVERIA ALLIACEA L.
Rabi A. Musah, Seokwon Kim and Roman Kubec
Department of Chemistry, State University of New York at Albany.
1400 Washington Avenue, Albany, NY USA [email protected]
A total of 18 organosulfur compounds originating from Petiveria
alliacea L. roots have been tested for their antibacterial and antifungal activities. These represent compounds occurring in fresh homogenates as well as those present in various macerates, extracts and other preparations made from P. alliacea. Of the compounds assayed, the thiosulfinates, trisulfides and benzylsulfinic acid were observed to be the most active, with the benzyl-containing thiosulfinates exhibiting the broadest spectrum of antimicrobial activity. The effect of plant sample preparation conditions on the antimicrobial activity of the extract is discussed.
RS
COOH
NH2O
CH2R = (1)
(2)CH2CH2OH
R1 SS
R2O
CH2CH2OHR1 = (4)R2 =
CH2CH2OH R2 = (5)R1 = CH2
CH2
R1 = R2 = R1 = R2 =CH2 CH2CH2OH(6) (7)
CH SO
(3)
CH2SO2HCH2SO3Na
(S)n R2R1
(18)(17)
Nonvolatile precursors:
Primary products:
Secondary products:
CH2CH2OHCH2
CH2
CH2CH2OH
R1 = R2 =
R1 = R2 =
R1 = R2 =
n = 1 (8), n = 2 (11), n = 3 (14)
n = 1 (10), n = 2 (13), n = 3 (16)
n = 1 (9), n = 2 (12), n = 3 (15)
,
,
, ,
,
,
140
P43-Mo
REDUCTIVE ALKYLATION OF 2-THIOPHENEACETONITRILE: A FACILE PROCESS LEADING TO THIOPHENE DERIVATIVES POSSESSING A CONGESTED C-2 SUBSTITUENT AND A NEW
Jing-Po Tsao and Hsing-Jang Liu
CLASS OF ALLENES
Institute of Chemsitry, Academia Sinica Nankang, Taipei 11529, Taiwan, R.O.C.
Department of Chemistry, National Tsing Hua University Hsinchu 30013, Taiwan, R.O.C.
A convenient process has been developed for the synthesis of thiophene derivatives possessing a quaternary carbon at C-2, using 2-thiopheneacetonitrile as a starting point. 2-Thiopheneacetonitrile was easily converted to a variety of fully substituted 2-thiopheneacetonitriles by direct or sequential dialkylation. As illustrated in the following scheme with a specific example (1→2), these compounds were found to undergo reductive alkylation readily at –100 oC using lithium naphthalenide as a reducing agent to give thiophene derivatives with a aternary carbon attached directly to
-2. The reductive alkylation process was shown to be highly temperature
quCdependent. When the reaction was carried out at a slightly higher temperature of –78 oC, the reductive alkylation was accompanied with an interesting ring opening process to give a new class of allenes. A specific example (1→3) is given below.
CNS
PhL.N., THF, -100 oC, 90 min
then PhCH2Br
SPh
Ph
PhSCH3
L.N., THF, -78 oC, 60 min
then CH3I
1
2
3
141
P44-Mo
ANALOGUES OF BIS-INDOLYLETHENES M.M. Krayushkin, V.N. Yarovenko, I.P. Sedishev, S.L. Semenov, I. V.
Zavarzin, S.V. Shorunov and F.M. Stoyanovich
Laboratory of Heterocyclic Compounds, N.D.Zelinsky Institute of Organic Chemistry, Russ spect, 119991, Moscow. Fax: (7-095)137-6939; e-mail: [email protected]
ian Academy of Sciences. 47, Leninsky pro
Bis-indolylethenes are characterized by a wide spectrum of biological activity. We developed methods for the synthesis of compounds containing the indole cycle (1-5) or a combination of thienopyrrole moieties (6-10).
NNH
N
S
N NN
NN R
N NNN
NN
NH
SMe Me NH
SMe Me NH
SMe Me1 2 3
NH
SMe
NH
R"
N N
R
R'
NH
NH
SN N
R
R'
Me
R"4 5
SNHMe
R'Het' = Het =
SMe
NH
R'; ; R,R' =Alk, Ar,CO2Me
OO
Het Het' HetHet
FF
F FFF
Het
S
Het Het
N
Het
OO
R
Het
O
Het
OO
6 7 8 9 10
A convenient method for the synthesis of thieno[3,2-b]pyrroles 11 as thienyl analogues of indoles, was developed.
SR
Me2N
O2N
R'SMe
O2N
R' S
NH
R
R'
RC(OMe)2NMe2 11[H]
R' = CO2Me; HetR = H,Me
142
P45-Mo
SYNTHESIS OF 3-ACYL-2,3-DIHYDROBENZOTHIAZOLES BY THE RING
CONTRACTION OF 2,4-DISUBSTITUTED 2,3-DIHYDRO-1,5-BENZOTHIAZEPINES
Albert Lévai
Department of Organic Chemistry, University of Debrecen, P.O.Box 20, H-4010 Debrecen, Hungary
Types and bulkiness of the substituents at positions 2 and 4 of the starting 2,3-dihydro-1,5-benzothiazepines are almost without influence on their ring contraction with varoius aldehydes. 3-Acyl-2,3-dihydrobenzothiazoles are obtained as sole isolable products under these reaction conditions. Structures of all new compounds have been elucidated by a combined utilization of different spectroscopic methods.
Ring contraction of 2,4-disubstituted 2,3-dihydro-1,5-
benzothiazepines afforded 3-acyl-2,3-dihydrobenzothiazoles under acylating conditions. This new procedure provides a general and efficient access to previously unknown benzothiazole derivatives.
N
S
Ac
RS
N
Ar
C CH
R
C OQ
1
12
3
45
6
7
8
9 7
6
5
4
1
2
3H
R: substituted phenyl, naphthyl, 3-chromonyl, styrylAr: substituted phenyl, naphthylQ: Me, Et, Ph
2
143
P46-Mo
PRE ES PARATION OF 2-ARYL BENZOTHIAZOL
Shahnaz Rostamizadeh S.A.Ghasem Housaini
Department of Chemistry , K.N.Toosi University of Technology , P.O.Box
15875-4416 Tehran , Iran
Benzothiazoles have been found to exhibit wide spectrum of biological activitie
ture of rubber, as fluorescent brightening agents for textiles plastics additives in textile dyeing and in the leather industry. The application of microwave energy in organic synthesis has attracted a substantial amount of attention in the past few years. Also, apart from traditional solution phase chemistry, the use of solid supports such as silica gel, alumina, has gained increasing attention in organic synthesis. These compounds have been prepared by different methods. In this report, we have prepared 2-substituted benzothiazoles 3a-g from the reaction of 2-aminothiophenol 1 and aldehydes 2 in the presence of PTSA on the surface of silica gel and graphite as solid support (Scheme 1). High yield, short reaction time, formation of only one product and easy workup are advantages of this method in comparison to other procedures.
3a C6H5 3e 3-NO2- C6H4 3b 4-NO2- C6H4 3f 3-Cl- C6H4 3c 4-Cl- C6H4 3g 4-OH- C6H4 3d 4-COOMe- C6H4 3h 4-CN- C6H4
Scheme 1 [1]Hutchinson,I.;Jennings,S.A.;Vishnuvajjala,B.R.;Westwell,A.D.;Stevens.M.FZ G.J. Med.Chem. 2002 ,45,744. [2]Takasu,K.; Inoue, H.; Kim, H,S.; Suzuki, M.; Shishido, T.; Wataya,Y.; Ihara, M. J. Med .Chem. 2002,45(5),995.
s. They have shown antitumor1 antimalarial2 and fungicide activity. They are also an important class of industrial chemicals. Many kinds of 2-substituted benzothiazoles are utilized as vulcanization accelerators in the manufac
NH2
SH
+
N
S
1
R CHOSiO2 / graphite
MWR, PTSA
2 3
144
P47-Mo
MICROWAVE ASSISTED PREPARATION OF 1,2,4-TRIAZOLE-3-THIONES.
Shahnaz Rostamizadeh Kambiz Mollahoseini
Department of Chemistry, K..N. oosi University of Technology ,
P.O.Box 158775-4416 Tehran , Iran Rosta .com
Many compounds bearing five memb ed heterocyclic rings in their struct g them,1,2,4-triaz n be used as antifungal 1,insecticidal, an atory antiasthmatic, antidepressant 2,and tuberculotherapeutic activities .In this paper we report on the p
d hydrazide (1) with alkyl r aryl isothiocyanante (2) and KOH (10%) on the surface of silica gel under
microwave irradiation (Scheme 1). High yield, short reaction time, formation of only one product and easy workup are advantages of this method in comparison to other procedures.
T
mizadeh@hotmail er
ure have an extensive spectrum of pharmacological activities. Amonoles have attracted considerable interest and ca
tibacterial, anti-inflamm
reparation of 4,5-di- substituted- 1,2,4- triazole-3-thiones for which antidepressant activity can be expected. These compounds have been prepared by different methods. In the present work they have been prepared in one stage from the condensation reaction of acio
R1 NHNH2 +
O
R2 NCS MW/
KOH(10%) NN
NS
R2
R1
H(1) (2) (3)
SiO2
Product R1 R2 Yield(%) 3a C6H5 C6H5 82 3b 4-Cl-C6H4 C6H5 88
[1] S. Rollas., N.Kalyoncuglu., D.Sur-Altiner, Y.Yegenoglu., pharmazie, 1993,8, 308. [2] J.M. Kane., M.W. Dudley., S.M. Sorensen P. Miller. J. Med. chem., 1988,31,1253.
3c C6H5 CH3 75 3d 4-Cl-C6H4 CH3 78 3e 4-NO2- C6H4 C6H5 90 3f CH3 C6H5 65
(Scheme 1)
145
P48-Mo
DISPROPORTIONATIONS OF S-SILYL AND S-ARSENIC DERIVATIVES OF THIOPHOSPHORUS ACIDS
Elvira S. Batyeva,1 Il’yas S. Nizamov,1,2 Boris E. Abalonin,2
1A. E. Arbuzov Institute of Organic and Physical Chemistry, Arbuzov Str. 8, 420088 Kazan, Russia
sphorus thioacids deri-ir
horus -
S- S-Trimethylsilyl S-
-ray
Il’nar D. Nizamov,2 Yan E. Popovich,1 Evgeniy S. Ermolaev1
2Kazan State Pedagogical University, Mezhlauk Str.1, 420021 Kazan, Russia
E-mail: [email protected]
There is considerable interest in tetracoordinated phovatives containing the P(S)SE (E = Si, As) structural fragment, due to thepossible use as synthetic intermediates for new organothiophospcompounds. The reaction of 2,4-bis(alkylthio)-1,3,2,4-dithiadiphosphetane2,4-disulfides with trimethyl(dialkylamino)silane has been found to givetrimethylsilyl S-alkyl(dialkylamido)trithiophosphates.ethyl(diethylamido)trithiophosphate was partially transformed into cyclic 2,4-bis(diethylamido)-1,3,2,4-dithiadiphosphetane-2,4-disulfide and trime-thyl(ethylthio)silane. The molecular and crystal structure of 2,4-bis(diethyl-amido)-1,3,2,4-dithiadiphosphetane-2,4-disulfide was established by Xsingle crystal diffraction.
In of this, S-diethylarsenic(III) aryl(dialkylamido)dithiophosphonates obtained in the reaction of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disul-fides with dialkylaminodiethylarsines was decomposed at 70oC for 1 hour to yield linear bis(diethylarsino) aryltrithiop
contast
hosphonates.
The crystal structure phenyl)trithiophosphonate was studied by X-ray single crystal diffraction.
of bis(diethylarsino) 2,4-di(3,5-di-tert-butyl-4-hydroxy-
he study was performed with the financial support of the Russian an
TFoundation for Basic Researches and Academy of Sciences of Tatarst(grant No. 03-03-96208).
146
P49-Mo
SYNTHESIS OF 3,4 DISUBSTITUED THIOPHENE DERIVATIVES VIA PALLADIUM CATALYSED CROSS COUPLING REACTIONS
Murat Gulcur
, Okan Sirkecioglu
Istanbul Technical University, Faculty of Science & Letters Departmen , Istanbul
y their
s
light
t of Chemistry, 80626, Maslak
Since the initial discovery of organic conducting polymers, verdiverse applications of these materials have emerged owing to remarkable electronic and photonic properties. Polythiophene and itderivatives are one of the important part of conducting polymer chemistry. Substituing 3 and 4 positions of thiophene with long wavelengthabsorbing chromophoric groups changes the UV absorption andluminiscence properties of the resulting polythiophene.
In this work, 3 and 4 substitued thiophene derivatives were synthesized by sequences of various organic reactions followed by Stille cross coupling reaction with high yield as depicted below.
S
R1 R2
R HR2: 6-Hydrox hthyl, 4-Methoxy [1] rohlic rg. Chem , 55, 29 995. [2] G.C. Collis, A.K. Burrel, J. Org. C 003, 6 74-8983
1: Br, OC 3 y Nap Phenyl
H. F h, W.Kalt, J. O . 1990 93-2hem. 2 8, 89
147
P50-Mo
SN2 v TO CHIRA ATES
Alber nez-
s E2 ON QUATERNARY CENTRES: AN EASY APPROACHL β 2,2-AMINO ACIDS FROM CYCLIC SULFAMID
to Avenoza, Jesús H. Busto, Francisco Corzana, Gonzalo Jimé
Osés and Jesús M. Peregrina
Depa esis Química de La Rioja (U.A.-C.S.I.C.). 26006-Logroño (SPAIN)
The development mmetric dihydroxylation
(AD) reaction to synthesize chiral 1,2-diols and the efficient method involving the Burgess five-membered cyclic sulfamidates from these 1,2-diols, have contributed to the expansion of the
ated for nucleophilic attack— and, to the best of our knowledge, it is the first time that such compounds have been opened by nucleophiles via SN2 reaction on the quaternary carbon. Competitive E2 reaction appeared when basic nucleophiles were used to give α-methylen- -
rtamento de Química. Universidad de La Rioja. Grupo de Sínt
of both the catalytic asy
-type reagent for preparing
chemistry of such reactive intermediates in organic synthesis.1 In connection with our research into the asymmetric synthesis of conformationally restricted amino acids, we focused our attention on two five-membered cyclic α-methylisoserine-derived sulfamidates. It was believed that these two compounds would be excellent chiral building blocks for the synthesis of α-methyl-β-amino acids by a SN2 reaction, as a key step.
We report here an easy synthetic approach to a varied collection of β2,2-amino acids.2 Although the synthesis and reactivity of several sulfamidates has been well documented, little is known about five-membered cyclic sulfamidates that are gem-disubstituted at the 5-position —the quaternary carbon activ
βalanines, but it was suppressed simply changing the amide group by the ester group in the cyclic sulfamidate.
O O
NOMe
Me
O
MeR1
Me
O
HOHO
NS OOO
MeO
O
MeR1
O
O O O
AD-mix-αSEt3N NO OMe
R1 = N(OMe)Me, OMe R1 = N(OMe)Me, OMe
Nuc
1
Burgess reagent
MeO NH
R1
Me R2H2N OH
Me R3
(SN2)
R = N(OMe)Me, OMeR2 = CN, N3, O-PNB, SMe, F R3 = CN, NH2, OH, SMe, F
1] R. E. Meléndez and W. D. Lubell, Tetrahedron, 2003, 59, 2581-2616.
] A. Avenoza, J. H. Busto, F. Corzana, G. Jiménez-Osés and J. M. eregrina. Chem. Commun., 2004, 980-981.
[[2P
148
P51-Mo
SYNTHESIS OF FUNCTIONALIZED TETRAHYDROFURANS FROM HYDROXY SULFINYL DIENES
Roberto Fernández de la Pradilla, Alejandro Castellanos, Mercedes Ureña
Instituto de Química Orgánica, Consejo Superior de Investigaciones Científicas Juan de la Cierva, 3. E-28006 Madrid, Spain.
Functionalized tetrahydrofurans are ubiquitous constituents of natural
and Alma Viso
products. In the past few years we have developed routes to access these systems from hydroxy sulfinyl dienes 1 that rely on nucleophilic and metal-catalyzed epoxidations.1 In this communication, we describe our recent efforts in this field that have led to carbohydrate precursors 2 and 3 and to the development of efficient and sterereoselective conditions to cleave the oxirane of substrates 4 to produce ketones 5.
SR
HO
O
p-Tol
O N
O
Bn O N
O
Bn
O
RΣ
OH
O O
RO
OH
1
2 3
5
SO
-TolS* =
O
RS*
O
ROH
p
4Σ = SO2p-Tol
[1] (a) Fernández de la Pradilla, R.; Méndez, P.; Priego, J.; Viso, A. J. Chem.
radilla, R.; tínez-Cruz,
L. A. J. Org. Chem. 2003, 68, 7755-7767.
Soc., Perkin Trans. 1 1999, 1247-1249. (b) Fernández de la PManzano, P.; Montero, C.; Priego, J.; Martínez-Ripoll, M.; Mar
149
P52-Mo
(BENZO)CYCLOBUTENONE ETHYLENEDITHIOACETALS AS PRECURSORS FOR HIGHLY SUBSTITUTED NAPHTHALENES
AND CYCLOPENTENONES Konstantin Benda, Wilk nn InsLeibnizkonstantin.benda@tu-
o Regenhardt, Ernst Schauma
titut für Organische Chemie, Technische Universität Clausthal, strasse 6, 38678 Clausthal, Germany
clausthal.de
Cyclobutenediones are well established as useful starting materials for the efficient synthesis of highly substituted quinones and aromatic compounds1.
Reported herein is an efficient preparation of substituted naphthalene derivatives via a sequence of hydrosilylation and Diels-Alder reactions using benzocyclobutenone ethylenedithioacetals as starting material and a method leading to cyclopentenones using unreduced cyclobutenones directly via formal [4+1]cycloaddition.
O OR3
R1= H, COOMe, CN, MeR2= OMe, Me
R3= OMe, Me, Ph, SiR3
O
SS DMPS-H
B(C6F5)3
ODMPS
S
S
O
SSR2
R3 R3
R2S
S
SS
ODMPS
EWG
R1
SS
SiR3
R2
dienophiles
heat carbenoids
Both processes work in a one-pot manner. Reaction with different dienophiles (both alkenes and alkynes) leads to naphthalenes in good yield (60 – 72 %). Heating of substituted cyclobutenones (usually in toluene at 95°C) and addition of different carbenoids (silylated diazomethanes) leads to cyclopentenones in excellent yields (> 92%). These compounds have potential as starting materials for further substitution, e.g. 1,2 addition o
rganometallics and subsequent Peterson olefination. f
o [1] L.M-Gayo, M.P.Winters, H.W.Moore J. Org. Chem. 1992, 57, 6896-6899.
150
P53-Mo
AS N YMMETRIC SYNTHESES OF α-SULFINYLPHOSPHONATES ITHE THIOLANE SERIES
Mihaela Guleaa, Piotr Kielbasinskib, Piotr Lyzwab, Marian Mikolajczyk,
Serge Massona
a La 07) University and ENSICAEN, 6, Bd Maréchal Juin, 14050, Caen, France. b Centre of Molecular an dies, Polish Academy of
ciences, Sienkiewicza 112, 90-363 Lodz, Poland.
boratory of Molecular and Thio-organic Chemistry (UMR CNRS 65
d Macromolecular StuS
[email protected]; [email protected]
Enantiopure β-sulfinyl phosphonates are useful chiral olefinating reagents for the generation of α,β-ethylenic sulfoxides, which can be used as asymmetric dienophiles or Michael acceptors. The first enantioselective synthesis of a 1-oxo 2-phosphonothiolane 2 had already been achieved via the [2,3]-sigmatropic rearrangement of the carbanion derived from di-(L)-menthy lsulfanyl)methanephosphonate.1 We now describe more direct and general ways to prepare nonracemic sulfoxides of the same series by the methods involving asymmetric oxidations of racemic or achiral thiolanes. Racemic 2-phosphonothiolanes 1 (R = ethyl, isopropyl, 2,2-dimethylpropane-1,3-diyl), prepared from 1-oxothiolane by a Pummerer-phosphorylation reaction,2 were treated with half an equivalent of (+)-(2S, 8aR)-8,8-dichloro-camphorsulfonyloxaziridine. A preferential oxidation of one of the enantiomers together with a diastereoselective formation of the trans-sulfoxides 2 was observed leading to enantioenriched 1 and 2.
l (ally
(RO)2PO
S (RO)2PO
S (RO)2P
O
S
O
0.5 equiv.
(+) 1
+
(+) 2racemic 1
(+)-oxaziridineSO
1) (CF3CO)2O
2) 2 (RO)3P CCl4, r. t.
2-Phosphono-2,3-didehydrothiolanes 3 were further prepared from e sulfoxides 2 under Pummerer conditions. Their enantioselective
xidation using the same oxaziridine led to the enantioenriched ethylenic thosulfoxides 4. A highly diastereoselective 1,4-addition of benzenethiol to these sulfoxides resulted in the formation of 1-oxo-2-phosphono-3-phenylthio-thiolanes 5 with three controlled stereogenic centers.
O O O
[1] P. Marchand, M. Gulea, S. Masson, M. Saquet, N. Collignon, Org. Lett. 2000, 2, 3757 [2] P. Marchand, M. Gulea, S. Masson, M.-T. Averbuch-Pouchot, Synthesis, 2001, 1623.
(RO)2P S(CF3CO)2O (RO)2P
O
S
O
ε Et3NPhSH
(RO)2P S
PhSCCl4, r. t.
ee% up to 98%
(+)-oxaziridine
3 4de% up to 98%
5
2
151
P54-Mo
N
Shigenobu Aoyagi, Ryo Kawamura, Kazuaki Shimada, Yuji Takikawa
g, an,
c.jp
Effe
ur previous research work revealed that thermal reaction of alkynyl
OVEL SYNTHESIS OF HEXAHYDROISOINDOLE DERIVATIVESUSING ALLENYLTHIOKETENES
Department of Chemical Engineering, Faculty of Engineerin
Iwate University., 020-8551, 4-3-5 Ueda, Morioka Iwate, Japiwate-u.aaoyagi@
cient and readily accessible synthetic methods for isoindoles,
intermediates of biologically active compounds, have been widely investigated. O
propargyl sulfides 1 in the presence of secondary alkyl amine affordes α,β,γ,δ−unsaturated thioamides in moderate yield. In this presentation we describe the application of the methodology to achieve hexahydroisoindole synthesis.
S R 2 R 1
R 2
R 1
o
o S N R 3
R 2
R 1 S
N R 3 R 1
H
R 2 S [ 3 , 3 ] N H R 3
[ 4 + 2 ]
1 2 3 4 Thermal reactions of 1 in the presence of allylamine afforded (E),(Z)-mixture of 3 in moderate yields along with the formation of thiophenes. Heating the (E),(Z)-mixture of 3 in refluxing toluene gave cis-hexahydroisoindole-2-thiones 4 exclusively in excellent yield. cis-Ring systems of 4 were determined by NOE experiments by 1H NMR. The analogous reactions using propargyl amine also afforded [4+2] adducts. The efficiency and selectivity of the indole synthesis would be attributed to the facile (E)/(Z) isomerization of 3 followed by the intramolecular [4+2] cycloaddition of favored isomers.
152
P55-Mo
REGIOSELECTIVE MICHAEL ADDITION OF THIOLS TO UNSYMMETRICAL FUMARIC DIESTERS OR ESTERAMIDES
Akio Kamimura, Norikazu Murakami, Hiroyuki Suzukawa, and Fukiko
Kawahara
Department of Applied Chemistry, Faculty of Engineering, Yamaguchi University, Ube 755-8611, Japan
Conjugate ad maric diesters was well controlled by the presence of lithium cation and one of the two possible
er
dition of thiols to unsymmetrical fu
regioisomers was prepared in a highly selective manner. Fumaric esteramides underwent the regioselective Michael addition that was controlled by the presence or absence of the base; either of the regioisomers was prepared as an almost diastereomerically pure form. To clarify the origin of the regioselectivity, the relative rates of the conjugate addition of thiol to acrylate derivatives were measured under competitive conditions. In the presence of base, ethyl acrylate gave the adducts much faster than acrylamide, while under non basic conditions acrylamide showed highreactivity than the ester.1
O1 RSH SR OO
1
t-BuO2CCO2Et t-BuO2C
CO2EtSR
RSH/RSLi(0.1 eq)CH2Cl2/-50 °C.
EtO2C NR
R2EtO2C N
R1
R2EtO2C
SRN
R
R2
RSHEt3N
The thio groups introduced here served as a leaving group and aconvenient stereoselective synthesis o -, γ- and δ-lactams was developed.
f β
EtO2C N
O
SPh
61%, 85:1
PhSH/Et3N Bu3SnH/AIBN
toluene
s >98/2
N
CO2Et
O
EtO2C N
OEtO2C N
O
95%, >98:2
SPhPhSH Bu3SnH/AIBN
tolueneslowaddition
N
CO2Et
O
68%, d
568%, ds = 5:1
[1] Kamimura, A. et. al. Tetrahedron 2003, 59, 9537; Tetrahedron Lett. 2002, 43, 7521; 2001, 42, 8497. 153
P56-Mo
HIGH DIASTEREOSELECTION IN TANDEM MICHAEL-ALDOL N-CINNAMOYLOXAZOLIDINE-2-TREACTION OF HIONES WITH
ELECTROPHILES MEDIATED BY LEWIS ACIDS
Tadashi Kataoka
, Hironori Kinoshita, Takashi Osamura, Kyosuke Yam abe
-alkoxy-2-(α-mercaptobenzyl)propionimides with three contiguous chiral centers.
amoto, Kazumi Mizuno, Tatsunori Iwamura and Shin-ichi Watan
Gifu Pharmaceutical University, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Recently, we reported the tandem Michael-aldol reaction of N-
cinnamoyloxazolidine-2-thiones with aldehydes in which four chiral centers were induced at once.1 Reactions with aldehydes using BF3·Et2O gave tricyclic compounds containing three contiguous chiral centers and a chiral bridgehead bound to four heteroatoms, while reactions with acetals in the presence of SnCl4 afforded 3
The results demonstrated that the intramolecular Michael addition of
the thione group to the enone moiety proceeded in different manners depending upon the Lewis acid used. [1] T. Kataoka, H. Kinoshita, S. Kinoshita, T. Osamura, S.-i. Watanabe, T. Iwamura, O. Muraoka and G. Tanabe Angew. Chem. Int. Ed. 2003, 42, 2889-2891.
154
P57
THE MODIFIED JULIA-KOCIENSKI OLEFINATION WITH 3,5-BIS(TRIFLUOROMETHYL)PHENYL SULFONES: APPLICATIONS
TO THE SYNTHESIS OF METHOXYLATED STILBENES
Diego A. Alonso
anta, Carmen Nájera and Montserrat Varea , Mónica FuensDepartamento de Química Orgánica and Instituto de Síntesis Orgánica (ISO). Facultad de Ciencias, Universidad de Alicante. Apartado 99, E-
03080 Alicante (SPAIN) [email protected]
Hydroxylated (E)-stilbenes are natural polyphenols widely
represented in nature which have become of great interest to chemists and biologists due to their wide range of biological activities. The phytoalexin resveratrol is the most important exponent of this family of compounds since exhibits unique and useful biological antioxidant, antimutagenic and lifespan extension properties.
The Julia-Kocienski olefination reaction has recently emerged as a powerful tool for the synthesis of alkenes.1 We have recently shown that the 3,5-bis(trifluoromethyl)phenyl sulfonyl (BTFP-sulfonyl) group,2 is an excellent activator for the synthesis of olefins through the Julia-Kocienski reaction.3 In this communication, we describe the application of this methodology to the stereoselective synthesis of resveratrol analogues (Scheme 1).
KOH or P4-t-Bu ArCHO
O2S
CF3
F3C +
Ar
OMe
MeO
r =
OMe OMe OMeS
OMe
OMe
The reaction, which takes place through a Smiles rearrangement,4 is performed under Barbier conditions employing KOH or the phosphazene base P4-t-Bu as bases, either at rt (KOH) or at –78 ºC for P4-t-Bu in THF as solvent. Good yields and (E)-selectivities of the corresponding stilbene derivatives are obtained under these reaction conditions. [1] Blakemore, P. R. J. Chem. Soc., Perkin Trans. 1, 2002, 2563-2585. [2] (a) Alonso, D. A.; Nájera, C.; Varea, M. Tetrahedron Lett. 2001, 42, 8845-8848. (b) Alonso, D. A.; Nájera, C.; Varea, M. Helv. Chim. Acta 2003, 85, 4287-4305. (c) Alonso, D. A.; Nájera, C.; Varea, M. Synthesis 2003, 277-287. [3] Alonso, D. A.; Nájera, C.; Varea, M. Tetrahedron Lett. 2004, 45, 573-577. [4] Truce, W. E.; Kreider, E. M.; Brand, W. W. Org. React. 1970, 18, 99-215.
A
OMeOMe
OMeOMe
OMe OMeOMe N
Scheme 1
155
![1 Asymmetric Synthesis of Chiral Sulfoxides - Wiley-VCH … · Asymmetric Synthesis of Chiral Sulfoxides ... see Refs. [2–7]). Enantiopure ... The enantioselective oxidation of](https://img.pdfslide.us/doc/110x75/5b5127a37f8b9ad8118ba0e6/1-asymmetric-synthesis-of-chiral-sulfoxides-wiley-vch-asymmetric-synthesis.jpg)
