GRAPHICAL ABSTRACTS

A NEW SYNTHESIS OF a-FUNCTIONALIZED UNSUBSTITUTED SULFONAMIDES

Tetrahedron Lert. 1990,31,1653

Franklin A. Davis,’ Pin9 Zhcu and 0. Sankar Lal Department of Chemistry. Drexel University, Philadelphia, PA 19104

Reaction of electrophiles with the dianion of camphorsutfonimines (1). atfords a-fundionalized unsu&fiMd sulfonamides in good to excellent yiekt fdbwlng hydrolysis.

(4-l 1) Bam t’=bCYB 2)~+

The Effect of Ligand Variation on the Rate of Cyclododecane Oxidation Under Modified GoAgg’* Conditions

Tetrahedron Lat. l9!JO,31,1657

+ lfgands -*

Li reduces J

and variation increases speed of oxidation up to 50 times or, for pyridine-Z-phosphonic acid, e rate to 0.

Elie About-Jaudet, Derek H. R Barton, Eva Csuhai and Nubar Ozbaiik Department of Chemistry, Texas A&M University, College Station, TX 77843

+

CoAKg" 0

Tetrahedron Left. l!BO, 31,166l TLC-CIMS : A HIGHLY EFFICIENT MASS SPECTRAL TECHNIQUE

FOR SYNTHETIC ORGANIC CHEMISTS Ajay K. Bose*, Keiko Tabei, and Vegesna S. Raju Department of Chemistry and Chemical Engineering Stevens Institute of Technology, Hoboken, NJ 07030, U.S.A.

A combination of thin layer chromatography with Chemical Ionization Mass Spectrometry has been developed. direct transfer of compounds from a TLC spot to a solids .probe is made by using a Carbowax 2OM pellet and valuable spectral data are obtained.

Tehahedron Len. l!BO,31,1665 CONNECTIONS TO THE MRECTED ortho METALATION STRATEGY. Pd(O)-CATALYZED CROSS COUPLING OF ARYL BORONIC ACIDS WlTH ARYL TRIFLATES Jian-min Fu and V. Snieckus” Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3Gl

1643

Tetrahedron L.ett. 1990,31,1669 SELECTIVE CLEAVAGE OF t-BUIYLDIPXENYLSILYL ETHERS

IN THE PRESENCE OF t-BUTYLDIMETHYLSILYL ETHERS.’

Mohammed S&b Shekhani.” Khalid Mohammed Khan,* Khalid Mahmood,’ pir Mozzam Shah,’ and Sohail Malik*b a) HBJ R-h htitute of Chunky, Univ. of Karachi. Karachi-32 Pakistan

b) De@. of Medicine and Lab. Medicine, Univ. of Washington. Seatie.

WA 98195, USA.

t-E?c)~ E m’.rs

R = (L- or l3-OH t-BuMe.#O

A convenient method for selective clew e of TBDPS (&utyldiphenylsilyl) ethers in the presence of TBDMS (t-bmyldime r ylsilyl) ethers has been described.

Tetrahedron L&t. 1!990,31,167 1 ALLYLK: WUF’Llffi BElWEEN ELE TROPHlLlC MOLYBDENUM AND NUCLEOPHlLlC IRON ALLYL &I WLEXES

S. R. Berryhill’ and J. G. Breitenbpcher Department of Chemistry and Biochemistry, California State University, Long Beach, Long Beach, CA 90840

Allylic coupling between [$pMo(&)(NO)(q3-allyl)]+ and CpFe(CO)&t -allyl) yields a dinuclear complex. The coupling occurs stereospecifically with respect to the molybdenum center.

1 +hexadiene

Tetrahedron L.&t. 1990,31,1675

N-HYDROXYPYRIDINE-ZTHIONE CARBAMATES. VII. INTERMOLECULAR ADDITION AND ADDITION-CYCLIZATION REACTIONS OF AMINIUM CATION RADICALS

Martin Newcomb* and M. Udaya Kumar X

Department of Chemistry, Texas A&M University College Station, Texas, 77843, USA It’ x

Dialkylaminium cation radicals frqm the title precursors K’ I: &

OEt

OEt h N added to enol ethers to give produets 7 and 8. Pyrmlidines 10 and 11 were formed from addition-cyclization reactions

R! 7:X=H

when one of the groups on nilrogen was allyl. x: x = S-2.pylidyl 10: X = S-2.pyridyl II: X = H

I Tetrahedron Lm. l!J90,31, 1679

HIGHLY STEREOSELECTIVE RADICAL ADDITION TO A TRISUBSTITUTED ALKBNE BY LOW TEMPERATURE PHOTOLYSIS OF THIOHYDROXAMIC ESTERS Daniel M. SCOU, Andrew T. McPhall and Ned A. Portef Department of Chemisby, Duke University, Durham, NC 27706, USA

~~~&&l; A:B > 125 : I : yield of A > 90%

1

1

I

1644

INHIBITION OF PLANT GLYCOSIDASES BY A D-GALACTURONIC ACID ANALOG

Tetraheakon Lett. 1990,31,1683

Michael K. Tong, Edward M. Blumenthal and Bruce Ganem* Department of Chemistry, Baker Laboratory, Cornell University Ithaca, New York 14853 USA

The aza-sugar shown was synthesized &om D-galactose. It inhibits galactosidases and galacturonases.

HO 0 HO-

HO

%

NH

HO

N-(a-AMiNoACYLOxY)-N-ARYLAM- Tetrahedron Lett. @9& 31,168s

ACIWATION OF AROMATIC AMINES To ULTIMATE CARCINOGENS BY AMINO ACIDS

Chris Meier and Gemot Boche* Fachbereicb Chemie, Univer&t Marburg, Hans-MeenwkStrage, D-3550 Marburg (FRO)

By means of the amine catalyzed N-so-acyl transfer reaction 4 g 5 we prepared from the amino acid derived N-(a-aminoacyl)- hydroxamic acids 4&47e the corresponding N-(a-amiooacyloxy)-N-arylamioes S, and trapped them in situ with (bii)nuckophiles to give the adducts 9.10 and 11, respectively. These model studies show that the a&ation to give ultimate carcinogens of aromatic aminesSi5alsopomii~ebyamiooacids.

Tetrahedron Len. 1990,31,1689 S& AT NITROGENz THB RIWXION OF .N%CYANO PHBNYL+-G-DIPHBNYLPHOSPIIINOYLHYDROXYLAMINB WITH N-ME-. A MODEL FOR THE REACTIONS OF ULTIMATR. CARCINOGENS OF AROMATIC AMINES WITH (BIO)NUCLBOPIIILES R6diger Ulbricb, Michael Famulok, Ferdinand Bosold and Gemot Bocbe* Facbbereicb Chemie, Univer&t Marburg, Hans-Mtcrwcinstra&, D-3550 Marburg (PRG) A kinetic study shows that the reaction of N-(4-fyanoph~)-O-~phcnylphosphinoyIhy 5 with N-m- 6, a model for the reactiom of ultimate carcinogens of aromatic amines with bionucleop~ follows the S$ me&a&m. The interme- diate formation of a nitreoium ion is excluded. Since the reactions of 0-acetyl-N-(4-bipheayi)Qdmx&nii 1, an ultimate car&w gen, with N-methylaniline 6 in sohreats of strongly merent polarity always give the same adducts l517,‘adduct formation should likewise follow a bimolecular me&a&m, the reaction between 1 and 6.

Tetrahedron Len. BPO, 31,1693

A MODEL COMPOUND FOR THE ULTIMATE CARCINOGEN OF THE PHBNACBTlN RELATED 4-BTHOXYANILINB

Chris Meier and Gemot Bocbe* Pachbereicb Chemie, Univer&t Marburg, D-3550 Marborg, FRG

In this communication we desaibe the synthesis of N-acetoxy4methoqwiKoe 7a, a model for the u&mate carcinogca of phenacc- tide 1. N-acetm 4, and the restion of 7a with dcaxyguanosio dG to give the adduct 10.7a and the n&ted 7b,c were also crapped ia situ with N-mcthyWline and dG to give the adducts g, 9 and 10, respectkely.

1645

Hetern-Diels-Alder reaction of substituted I-oxabutadienes and Terrahedron Lert. 19!IO,31,1697 ‘

2-ethoxyvinylacette. An entry to various natural occurring carbohydrates. L. F. Tietze* ad U. Hartjiel, Inst. $ Org. Cltem., Univ. Gdttingen, Tammannstra~e 2, D-3400 Gtittingeu, F R G. Hetero-Diels-Alder reaction of the enamino ketones 1 and vinyl ethers 2 yields the dihydropyrans 3 and 4, from which ezoaminuroic acid and desosamine derivatives are obtained.

R4 R5 ;I< T t Et0

1 2 3 1

AN EFFICIENT M FOR ING YYr

FmC-MINO A& TO lMNWYl-MIWISED LID gllppoRTS

Tetrahedron Lett. 1990,31,1701

Birgit Blankemeyer-Menge, tbnfred Nimtz and Ronald Frank GBF (Gesellschaft fiir Biotechnologische Forschung mW), Mascheroder Weg 1, D-3300 Brauhschweig, FRG

Fmoc-NH-CHR-COOH t HO-@ + +&CA%. + $ l Fmoc_NH_CHR_~_O@

THE PHOSPHAZO ROUTE TO 2-ALKENAMIDES Tetrahedron Lett. l!NO,31,1705 FROM ACRYLIC ACID AN0 ITS DERIVATIVES

Jest Cabral, Pierre Laszlo*, We-These Montaufier and SLalatiana Randriamahefa Laboratoire de Cbimie fine, biomimtique, et aux interfaces. Cole Polytechnique, 91128 Palaiseau, France

2-alkenamides are prepared via in-generated phosphazo compounds, issued from primary amines :

- 3 + 2 5 RNH2 + PC& RN&.HC; RN’;~.NHR

-HP02

0, 2 &NHR

0

CYCLOADDIlIflN DIPIJLAIRE I,3 DES 44RYLIDENES DXAZDL-5- ONE AVEC LA IlJPIIENYLNITI~lLIMINE N. OARA et M. SIJLI~-~AIJUI

Tetrahedron L&t. 1990,31,1709

Laboratoire de Cycloaddition, DBpartement de Chimie, fscult6 des sciences Rnbet (Maroc)

1646

Tetrahedron Len. l!J90,31.1713 ELECTROCHEMICAL SYNTHESIS OF THE VINYLOCS OF N-ACYL N,O-ACETALS AND THEIR REACTIVITY D. Fasseur, B. Rigo ,P. Cauliez M. Debacker and D. Couturier HEI, 13 rue de Toul, 59046 LILLE, FRANCE; USTL, 59655 Villeneuve d'Ascq, FRANCE

Anodic oxydation of f3-enaminoesters derived from pyroglutamic acid gives vinylogs of N-acyl N,O-acetals, which can react with amines, alcohols and silylated emines.

TOTAL SYNTHESIS OF BRANCHED-CHAIN HIGHER-CARBO Tetrahedron L.&t. l!EJO, 31,1717

SUGARS. FIRST SYNTHESIS OF CALDOSE, CALDITOL AND 4-DEOXYCALDITOL STEREOISOMERS. Suruliappa Jeganathan and Pierre Vogel*, Secti& de chimie de l’Universit6 de Lausanne, 2, rue de la Batre. CH-1005 Lausanne, Switzerland.

The branched nonitols 20 and 22 have been derived from 3 and (+)-4

A SIMPLE SYNTHESIS OF OXAZOLIDINONES IN ONE STEP Tewahedron L&t. 1990,31,1721

FROM CARBON DIOXIDE.

Jean Found, Christian Bnmeau and Piexre H. Dixneuf

Laboratoire&ChimiedeCoordinationOrganique-CNRSURADOQ15-CampusdeBeaulieu,Universi~deRennes,

35042Re~1esCedex(F1ance).

CH,

H-C-C-d-OH w

bH,

+ co, + RNH, PR3 ) cat.

R-NKo 0

A NOVEL REACTION FOR THE FUNCTIONALIZATION OF Tetrahea’ron Lett. 199&31,~723

EPOXY RESINS: NEW REGIO- AND CHEMOSELECTIVE RING-OPENING OF EPOXIDES WITH ARYL SILYL ETHER CA!i'ALYZED BY CESIUM FLUORIDE

Yoko Nambu and Takeshi Endo Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 227, Japan

RO- + PhOSiMeg

CsF (2 mol%)

- RmOPh ‘0’ 130 'C, 1 h dSiMe3 High yields with high regio-

and chemoselectivities.

1647

Tetrahedron ktt. 19!%3I, 1727 * A LASER-SPECIFIC C-C BOND FORMATION OF BICBROMOPHORIC COMPOUNDS Akihiko Ouchi.* and Akira Yabe National Chemical Laboratory for Industry, Tsukuba, Ibaraki 305, Japan

KrF excimer laser fluence of ca. >1016 photon*cm'2*pulse'1 is necessary for the- reaction.

Tetrahedron Lett. 1~,31,1731 TOTAL SYNTHESIS OF THE ABLYCONE OF VENTURICIDINS AANDB ---I, SYNTHESIS OF C,-C,‘, SEGMENT

Hiroyuki Akita,* Harutami Yamada, Hiroko Matsukura, Tadashi Nakata, and Takeshi Oishi*

RIKEN (The Institute of Physical and Chemical Research) 2-1, Hirosawa, Wako-shi, Saitama 351-01, Japan

The C -C segment corresponding to the bottom half (3f 3? t n uricidins A and B was synthesized by a strategy based on the biosynthetic consideration.

TOTAL SYNTHESIS OF THE ACLYCONE OF VENTURICIDINS A AND B ---II

I Tetrahedron L&t. l9%,31,1735

Hiroyuki Akita,* Harutami Yamada, Hiroko Matsukura, Tadashi Nakata, and Takeshi Oishi*

RIKEN (The Institute of Physical and Chemical Research) 2-1, Hirosawa, Wako-shi, Saitama 351-01, Japan

The aglycone of venturicidins A and B was synthesized via intramolecular Wittig-Horner reaction of the ester from C,-C,4 and C,5-C27 segments.

Tetrahedron L&t. 19% 31,1739 CONJUGATE ADDITIOY ~ REACTION OF ORGANO-

LITHIUMS TO NAPHTliALENECARBOXYLATES

K. Tomioka,* M. Shindo, and K. Koga, Faculty of Pharmaceutical Sciences, University of Tokyo, Tokyo 113, Japan

Conjugate addition of or anolithium with BHA esters of l- and 2-naptU F alenecarboxylic acids afforded dihydronaphthalanbs in quantitative yield.

1648

DRAMATIC ENANTIOSELECTIVITY CHANGE IN DIHYDROXYLATION OF OLEFINS WITH CHIRAL AMINE-OSMIUM TETROXIDE COMPLEX

K. Tomioka,* M. Nakajima, and K. Koga, Faculty of Pharmaceutical Sciences, University of Tokyo, Tokyo 113, Japan

Tetrahedron L&t, l!EJO, 31,174l

;;D-.x-Nz+;

1 Ar=Ph X=-(cH&- 2 Ar = 3sXylyl x = -(cH&- 3 Ar=Ph X=-(cH&-

A slight structural modification of chiral amine 1 to 2 4 Ar=Ph x= caused a dramatic enantioselectivity change in dihydroxylation of olefin with osmium tetroxide. 5 Arsph x=

Tetrahedron L.&t. 1990,31,1743 ASYMMETRIC ALLYLIC AMINATION CATALYZED BY CHIRAL FEBROCENYLPHOSPHINE-PALLADIUM COMPLEXES Tamio Hayti* and Kohei Kishi, Camtysis Research Center, Hokkuiab University. Kitaku, Sapporo 060. J@m AkihirO YamamX~ and Yoshihiko Ito,* Department of Synthetic Chemistry, Kyoto University, YosMda, Kyow 606, Japan

PhCH2NH2 Me l

MewOAc PdlL’ r”(

+ OH

THF NHCH2Ph

OH 94%ee(S) 9713

Tetrahedron ktt. m.31,1747 NOMENCLATURE OF AMERlCAN COCKROACH SEX PHEROMONES C.J. Persoons’ and F.J. Rkter, Department of Siibgy. MO, D&t, The Netherfands P.E.J. Verwiel. Prins Maurits Laboratory, TNO. Rijswijk, The Netherlands H. Hauptmann. lnstkut ftir Organische Chemie, Universitat Regensburg. West Germany K. Mod, Department of Agricultural Chemistry, Unlverslty of Tokyo, Japan

. . The c&mist&of the American cockroach sex pheromone is reviewed. New names are proposed for the following compounds:

Tetrahedron L.ett. 1990,31,175 1

NEW CHLOROPHYLL FOSSILS FROM MOROCCAN OIL SHAL PORPHYRINS DERIVED FROM CHLOROPHYLL q OR A RELATED PfGMENT 7 J. Verne-Miimer, R. Ocampo. H.J. Callot’ and P. Albrecht’, DQpartement de Chimie. Universite Louis Pasteur, 1, rue Blaisa Pascal, 67000 Strasbourg. France.

Petroporphyrins showing both a free C-7 position and a C-13 to C-17 substitution pattern typical of chlorophyll c fossils were isolated from two Cretaceous Moroccan oil shales. They may arise from a still unknown chlorophyll, 7-formylchlorophyll c or chlorophyll 9.

.ES.

coon

. I

Tekhedron Len. 1990.31,177 1 Thiamine Coenzyme Models Imidazolinium Ylides and the Reactions of 2-@Iydroxyalkyl)imidax4ines Raymond C.F. Jones * and John R. Nichols (Chunisrq Department, Nottingham University, Nottingham NG7 2RD, U.K.)

1. Mel; 2. NuH

JSIGHLY STEREOSELECTIVE ADDlTION OF ALKYLCOPPER Tetrahedron Left. 1990,31,1775

REAGENTS TO N-ACYLIMINIUM IONS. ENANTIOSELECTIVE SYNTHESIS OF TRANS-2-BUTYL-5-HEPTYLPYLPYROMDM.

Marco Skrinjar, Lam-G. Wistrand. Organic Chemistry 3, University of Lund, Chemical Center, P. 0. B. 124, S-221 00 Lund, Sweden.

Tetraheakon L&t. l!EJO,31,1779 RYDROXYL?LTION OF SATURATED RYDROCAREONS BY MAGNBSIDM HONOPBROXYPRTHAIATB CATALYSSED BY HANGANBSR PORPJ3YRINS Cecilia Querci, and Marco Ricci* Isfiluto G. Doncgani S.p.A., 28100 Novara, Italy

Magnesium monoperoxyphthalate is a very efficient oxygen donor for the manganese porphyrins catalysed hydroxylation of alkanes under mild conditions. Turnover rates up to 80 cycleslmin are observed.

Tetrahedron Lett. 1990,31,1783 STEREOSELECTIVE SYNTHESIS OF (9S,lZR,13S~

TRlHYDROXYOCTADECA(IOE,152)-DIENOIC ACID

M K Gut-jar* and A Sekar Reddy Indii Institute of Chemical Techno@y, Hyderabad 500 007, lndii

1

OH

1651