Li Transmetalation Reactions of a Dilithium Complex Snddata.over-blog.com/xxxyyy/3/59/81/73/Archives-2009/Cahier2009-6-.pdf · Ti Cyclopentadienyl-amidinate Titanium Imido Compounds

Bibliographic Notebooks For Organometallic Chemistry 2009, 27, ( 6)

Transmetalation Reactions of a Dilithium ComplexLi

CHEN, X.; GUAN, L; EISEN, M. S.; LI, H.; TONG, H.; ZHANG, L.; LIU, D.

HJ

NR CHSiMe3

Li OEt2N RMe3SiHC

LiEt2O

R = H, Me

R'CN

R'= tBu, PhN

R'

NSiMe3

LiN

Li

R'

N

R

Me3SiR

N

Ph

NSiMe3

Cu

CuCl Cu

N

Ph

N SiMe3

N

Ph

NSiMe3

SnCl3

N N

Ph

SiMe3

NN

Ph

Me3SiCoor

orSnCl4

or CoCl2or CuCl

SnCoCu

Eur. J. Inorg. Chem. 3488 34942009 -, , 23 ,

Lithiation of N-Alkyl-( o-tolyl)aziridinesLi

DAMMACCO, M.; DEGENNARO, L.; FLORIO, S.; LUISI, R.; MUSIO, B.; ALTOMARE, A.

CC

Me

N

Me

N

Me

E

O

NHMe

R'R

sBuLi/TMEDATHF, -78°C, 30 min.

then E+

(E+ = D2O, MeI, PrI,RCOR' and RCHO)

Yields = 21 - 95%

for E+ = RCOR' or RCHO

AcOH, 25°C, 4 - 6h

R, R' = H, tBu, Ph, Ar

Yields = 60 - 98%

J. Org. Chem. 6319 63222009 74 -, , 16 ,

Solution Structure of 1-MethoxyallenyllithiumLi

Combined computational and 13C-NMR study was reported.

DIXON, D. D.; TIUS, M. A.; PRATT, L. M.

CC

Li

OMe

Li

OMe

Li

OMe

Li

OMe

n

2 4 6

+ +

J. Org. Chem. 5881 58862009 74 -, , 16 ,

Carbolithiation of Conjugated Enynes Li

Reactional sequence was carried out in a microflow system.

TOMIDA, Y.; NAGAKI; A.. YOSHIDA, J.-I.

CC

Br

RR

SiR3

Ar (or HetAr)

ArnBuLi R3SiCl

integrated microflow system

Yields = 47 - 82%R = H, Me, F, OMe, Ph

Org. Lett. 3614 36172009 11 -, , 16 ,

1


Synthesis of Diaminocarbenes via Li/Cl ExchangeLi

SNEAD, D.; GHIVIRIGA, I.; ABBOUD, K. A.; HONG, S.

CC

NN+

Cl

NN

NN

BF3

NN

Pd ClNMe2N

N

M

Cl

BF4-

. .

BuLi, THF

-78°C, 1h

M = Rh, Ir

Org. Lett. 3274 32772009 11 -, , 15 ,

One-Pot Homologation of Aldehydes to Carboxylic AcidLi

MCNULTY, J.; DAS, P.

CC

(MeO)2P(O)

(MeO)2P(O) Li

NMe2

(MeO)2P N

O

R

RCHO RCH2COOH 48% HBr

100°C, 10 min

Yields = 75 - 90%R = Ar, Alk

-78°C to rt, THF

Tetrahedron 7794 78002009 65 -, , 37 ,

Reaction of 2-(Chloromethyl)phenyl Isocyanides with OrganolithiumsLi

KOBAYASHI, K.; IITSUKA, D.; FUKAMACHI, S.; KONISHI, H.

CC

ClR

R' NC NH

R"

R

R'

R = H, MeR' = H, Cl

R" = Alk, Ar

12 ExamplesYields = 49 - 72%

R"Li (3 eq), THF,

-78°C, 2h

Tetrahedron 7523 75262009 65 -, , 36 ,

Methylation of Gem-BromofluorospiropentanesLi

AVERINA, E.; SEDENKOVA, K. N.; BORISOV, I. S.; GRISHIN, Y. K.; KUZNETSOVA, T. S.; ZEFIROV, N.

CC

R

RR

R

R

BrF

R

12

3

4 56

R

RR

R

R

BrMe

R

12

3

4 56

R

RR

R

R

R

12

3

4

5

6MeLi, Et2O

-10 to 0°Cor

or rearrangementR = cycloalkyl, H, CH3, Ph, Ar

Tetrahedron 5693 57012009 65 -, , 29-3

,

2


Synthesis of Indazoles Using Diazo(trimethylsilyl)methylmagnesium BromideMg

HARI, Y.; SONE, R.; AOYAMA, T.

AE

R1 R2

O

NH

N

OR R1

R2

1) Me3SiC(MgBr)N2, THF, -78°C, 1.5h

2) , KF, [18]crown-6, THF, rt, 24h

R1 = Ph, 4-MeOPh, 4-CF3Ph, 2-Pyridyl, 2-thineyl, i-PrR2 = Ph, Me, Et, HR = H, SiMe3

SiMe3

OTf Yield = 43 to 82%

Org. Biomol. Chem. 2804 28082009 7 -, , 13 ,

Friedländer and Friedländer-Borsche Quinoline SynthesesCe

CAN catalysis avoids the use of harsh basic or acidic conditions and allows double condensations

SRIDHARAN, V.; RIBELLES, P.; RAMOS, P.; MENENDEZ, J.C.

OS

O

NH2 N N

Ce(NH4)2(NO3)6 (15%)

EtOH, reflux, 2 h.

85%

J. Org. Chem. 5715 57182009 74 -, , 15 ,

Nd(OTf) 3-Catalyzed Cascade Reactions of Vinylidenecyclopropanes with EnynolNd

YAO, L.-F.; SHI, M.

OC

R1

R2

R5R6

R4R3

C6H5

R7'

HO R7+

40-95% yield

R3

R4

R1

R2

R6R5

R7

C6H5R7'

Nd(OTf)3

CH2Cl2, rt

R1-R6 = aromatic or aliphatic groupsR7 = aromatic group

Eur. J. Org. Chem. 4036 40402009 -, , 24 ,

Tandem SmI2-Induced Nitrone ββββ-Elimination / Aldol-Type ReactionSm

RACINE, E.; PY, S.

AE

NOBn

OBnR1

R2

OBn

O

N Me

OBnR1

R2

OBn

O

SmI2, H2O

THF, -78°C

R1, R2 = H, OBn Yield = 50 to 88%

Ethyl Acrylate or Cyclopentanone

Org. Biomol. Chem. 3385 33872009 7 -, , 16 ,

3


Synthesis of Chiral Cyclobutanols and Cyclopentane DimersSm

Keto-olefin cyclisations of carbohydrate-derived unsaturated ketones; critical addition order of reagents.

WILLIAMS, D.B.G.; CADDY, J.; BLANN, K.; GROVE, J.J.C.; HOLZAPFEL, C.W.

GJ

O

PivO

O

OO

OEt

HOO O

O

OHOH

HPivO OPiv

CO2EtEtO

2C

SmI2, THF, HMPA

33%

Synthesis 2009 20142009 -, , 12 ,

Eu(III) Macrocyclic Trinucleotide Conjugate : Synthesis and UseEu

ESCUDIER, J.-M.; DUPOUY, C.; FOUNTAIN, M. A.; DEL MUNDO, I. M. A.; JACKLIN, E. M.; MORROW, J. R.

AE

N N

N N

O

H2N

H2NO

CH3

O

NH2

Eu3+

Org. Biomol. Chem. 3251 32572009 7 -, , 16 ,

Enantioselective Aminolysis of meso AziridinesTi

PERUNCHERALATHAN, S.; TELLER, H.; SCHNEIDER, C.

CY

N PhNHPh

NHPh

Ph NH2+

Ti(OtBu)4 (10 mol%)(R)-binol (22 mol%)CH2Cl2, –40 ºC

(1.1 equiv)92%

98% ee

Angew. Chem. Int. Ed. 4849 48522009 48 -, , 26 ,

Synthesis of Heterometallic Nitrido ComplexesTi

Single cube [MTi3N4] or corner-shared double cube [MTi6N8] structures observed

GARCIA-CASTRO, M.; MARTIN, A.; MENA, M.; YELAMOS, C.

PLA

TiNH

Ti

NHTi

NHN

Ti = TiCp*

[M(NR2)n]

M = Sb, Bi (group 15)

M = Ge, Sn, Pb (group 14)

R = alkyl, SiMe3

M = Ga, In, Al (group 13)heterometallic nitrido

complexes

GaInAlGeSnPb

Chem. Eur. J. 7180 71912009 15 -, , 29 ,

4


Titanium(III)-manganese(II) ClusterTi

JERZYKIEWICZ, L.B.; UTKO, J.; DUCZMAL, M.; SOBOTA, P.

GN

Ti

O

Mn

O

O

Cl

O

O

O

O

Ti

O

ClO

Cl

MnO

O

O

Ti

O

Mn

O

O

Cl

O

O

O

O

Ti

O

ClO

Cl

MnO

O

O

Cl

Cl

Mn

Dalton Trans 5450 54522009 -, , 28 ,

Cyclopentadienyl-amidinate Titanium Imido CompoundsTi

GUIDUCCI, A.E.; BOYD, C.L.; CLOT, E.; MOUNTFORD, P.

GN

R R

RR

Ti

N

N N R

R R

R

Dalton Trans 5960 59792009 -, , 30 ,

Titanium and Zirconium Hydrazido ComplexesTi

WILLNER, A.; NEUMANN, B.; STAMMLER, H.-G.; MITZEL, N.W.

GN

Ti

Me2N

O

Si

NMe

Me2N

Me

Me

Zr

Dalton Trans 6280 62822009 -, , 32 ,

Mono(aryloxido)Titanium(IV) ComplexesTi

Application in the selective dimerization of ethylene is described.

CAZAUX, J.-B.; BRAUNSTEIN, P.; MAGNA, L.; SAUSSINE, L.; OLIVIER-BOURBIGOU, H.

HJ

Me

tBu

OH

R

Me

tBu

O

R

Ti

PrOi

OiPr OiPr

Ti(OiPr)4, Et2O

Me

tBu

OM

R

TiCl(OiPr)3, THF

M = Na, Li

R = CMe3, CMe2Ph, CH2NMe2, CH2NMe(CH2Ph), CH2N(CH2Ph)2

NaLi

Eur. J. Inorg. Chem. 2942 29502009 -, , 20 ,

5


New Aryloxy and Benzyloxy Derivatives of TitaniumTi

Application in the polymerization of ε-caprolactone and δ-valerolactone is describedGOWDA, R. R.; CHAKRABORTY, D.; RAMKUMAR, V.

HJ

Ti(OiPr)4 + [Ti(OAr)a (iPrO)b(iPrOH)c]toluene

(a,b,c) = (4,0,0) or (4,0,1) or (2,2,0)

ArOH

18 different aryl groups

Eur. J. Inorg. Chem. 2981 29932009 -, , 20 ,

Stereochemistry of the Cyclopropanation of NitrilesTi

Intermolecular reaction are less stereoselective

ASTASHKO, D.; LEE, H. G.; BOBROV, D. N.; CHA, J. K.

BPH

NCN

Bn

R1

R2

NBn

NH2

H

R2

R1

ClTi(Oi-Pr)3c-HexMgCl

Et2O52-62%

R1 = H, R2 = MeR1 = Me, R2 = H

Mg

J. Org. Chem. 5528 55322009 74 -, , 15 ,

Titanium and Zirconium ComplexesTi

ELO, P.; PÄRSSINEN, A.; NIEGER, M.; LESKELÄ, M.; REPO, T.

GN

O O

NO

R

MCl Cl

M= Ti, Zr2

Zr

J. Organomet. Chem. 2927 29332009 694 -, , 18 ,

Olefinic-Amide and Olefinic-Lactam CyclizationsTi

ZHOU, J.; RAINIER, J. D.

OC

NTs

O

( )n NTs

( )nTiCl4, Zn, TMEDA

PbCl2, THF

CH3CHBr2

n = 1-4 60-82% yield

ZnPb

Org. Lett. 3774 37762009 11 -, , 16 ,

6


2-(Arylthio)benzoatesTi

IQBAL, I.; IMRAN, M.; RASOOL, N.; RASHID, M. A.; HUSSAIN, M.; VILLINGER, A.; FISCHER, C.; LANGER, P.

CC

SAr OSiMe3

OMe R R'

O O

X

R'R

OSAr

OMeTiX4 (1.5 eq), 14h

CH2Cl2, -78°C to rt+

Numerous Examples Yields = 33 - 58%

Tetrahedron 7562 75722009 65 -, , 36 ,

Ti-Mediated Intermolecular Alkyne-Carbonate CouplingTi

WOLAN, A.; CADORET, F.; SIX, Y.

CC

R R'

O

R"O OR"

H

R R'

CO2R" R, R' = Alk, Ar, TMS

Numerous Examples Yields = 12 - 90%

Ti(OiPr)4 (2 eq),cC5H9MgCl (3 eq),

Et2O, 0°C, 15 min then H3O

+

+

(1 eq)

(1 eq)

Tetrahedron 7429 74392009 65 -, , 36 ,

Ligand-Controlled Zirconocene Mediated C-C Bond Cleavage of allylcyclopropanesZr

Selective cleavage of both reactive and inert C-C bonds

WANG, C.; DENG, L.; YAN, J.; WANG, H.; LUO, Q.; ZHANG, W.-X.; XI, Z.

PLA

BrZrCp2BrBr

ZrCp2

Cp2Zr(II)Et

Cp2Zr(II)

Cu

Chem. Commun. 4414 44162009 -, , 29 ,

Hexanuclear Zirconium MacrocycleZr

FITZGERALD, M.; PAPPAS, I.; ZHENG, C.; XIE, Z.-L.; HUANG, X.-Y.; TAO, S.; PAN, L.

GN

Synthesis, isolation and characterization ofa hexanuclear zirconium metallocycle

Dalton Trans 6289 62912009 -, , 32 ,

7


Stereoselective Synthesis of ββββ-HydroxyallenesZr

Many other examples

ZHOU, Y.; CHEN, J.; ZHAO, C.; WANG, E.; LIU, Y.; LI, Y.

BPH

Cp2ZrCl2+

2 EtMgBrCp2Zr

RPh

THF Cp2Zr

R

Ph

R'CHO R

OH

PhR

Et

major isomer

Mg

J. Org. Chem. 5326 53302009 74 -, , 15 ,

Ansa-zirconocene ComplexesZr

KLOSIN, J.; KRUPER, W. J.; PATTON, J.T.; ABBOUD, K.A.

GN

Si ZrCl2

NR2

R2N

J. Organomet. Chem. 2581 25962009 694 -, , 16 ,

Regio- and Stereoselective Synthesis of Multisubstituted Vinylsilanes via ZirconacyclesZr

NISHIHARA, Y.; SAITO, D.; TANEMURA, K.; NOYORI, S.; TAKAGI, S.

OC

R3Si Ph

"Cp2Zr" PhR3Si

E

OTBS1.

2. E+

E = H, I, aryl, methyl, benzyl, alkynyl, allyl

regio-, stereoselectivity: > 99%

Si

Org. Lett. 3546 35492009 11 -, , 16 ,

Zirconium-Mediated Selective Synthesis of 1,2,4,5-Tetrasubstituted Benzenes Zr

LI, S.; QU, H.; ZHOU, L.; KANNO, K.; GUO, Q.; SHEN, B.; TAKAHASHI, T.

OC

R1 SiMe3

R2 R3

2 "Cp2Zr"

CuCl

TBAF+

R1

R1 R3

R2

Cu

Org. Lett. 3318 33212009 11 -, , 15 ,

8


Dinuclear Hafnium(IV) and Zirconium(IV) ComplexesHf

Catalytic dehydrogenation of cyclooctane

NOMIYA, K.; SAKU, Y.; YAMADA, S.; TAKAHASHI, W.; SEKIYA, H.; SHINOHARA, A.; ISHIMARU, M.; SAKAI, Y.

GN

Synthesis and characterization of two dinuclear HfIV and ZrIV complexes sandwiched between 2-mono-lacunary a-Keggin polyoxometalates

Ti

Dalton Trans 5504 55112009 -, , 28 ,

Olefin Epoxidation with Mo catalystsMo

MOHAN KA,NDEPI, V.V.K.; PONTES DA COSTA, A.; PERIS, E.; ROYO, B.

RE

R1 R1

R1

R1

R2

R3

R4

PhN

N

Mo COCO

I

Organometallics 4544 45492009 28 -, , 15 ,

Stereospecific Mo(VI)-Catalyzed Transformation of DeoxysugarsMo

Mutual isomerization of a great variety of 5-, 6-, and 7-deoxysugars in a microwave field has been realized.

HRICOVINIOVA, Z.

PL

OHO

HO

OH

OH

CH3OHO

HO OHOH

CH3 Mo(VI)

ratio I:II = 1.5:1 by heating

ratio I:II = 2.3:1 by microwave

I II

Tetrahedron Asymm. 1239 12422009 20 -, , 11 ,

Allyl W ComplexesW

SEMPRONI, S. P.; GRAHAM, P. M.; BUSCHHAUS, S. A.; PATRICK, B. O.; LEGZDINS, P.

RF

W

ON

RR'

E

E+C,Si

CPh3+

R' CPh3R


9


Resolution of Chiral Metal Tetrahedral CompoundsW

ZHAO, Q.; HUA, B.; ZHANG, Y.; LI, W.; XIA, C.; YIN, Y.

PL

CH2OHC

W(CO)2CpCOCH3

Co(CO)3

HC

CH2OHC

W(CO)2CpCOCH3

Co(CO)3

HC

CH2OCOCH3C

H3COCCp(OC)2W

Co(CO)3

CH

lipase Novozym 435

CH2=CHOCOCH3DIPE

50%, ee 31% 42%, ee 92%

+

Co


Photochemical Behaviour of Complexes with Carbamate GroupsMn

Toward photochromic systems due to reverse dissociation and recombination of CO.

TELEGINA, L. N.; EZERNITSKAYA, M. G.; GODOVIKOV, I. A.; BABIEVSKII, K. K.; LOKSHIN, B. V.; STRELKOVA, T. V.;BORISOV, Y. A.; LOIM, N. M.

HJR

C

CH3

N C

O

H

H

C

H3C

N

CO

H

HMnMn

OCCO

CO OCCO

+ CO

OtBu

OtBu

CrimsonColorless

hν / rt

Pt

Eur. J. Inorg. Chem. 3636 36432009 24 -, , ,

Visible Light Enhanced Selective Reductive Elimination Mn

ca. 15 times faster than the reaction in the dark.

KOMIYA, S.; EZUMI, S.; KOMINE, N.; HIRANO, M.

HJR

Ph

N N

Pt Mn(CO)5

Me Me

Me-Mn(CO)5 +

Me

N N

Pt

Ph

tButBu tBu

tBu

hν (> 500 nm)

C6H6, 20 °C


Synthesis of αααα,ββββ-Unsaturated Esters and Amides Promoted by Rieke ManganeseMn

Feature article; 66 examples, yields: 68-92%; stereoselective olefination reactions.

CONCELLON, J.M.; RODRIGUEZ-SOLLA, H.; DEL AMO, V.; DIAZ, P.

GJ

H

O O

Cl

Cl

OEt

O

OEt

Active Mn prepared from Li2MnCl

4

+

83%

Mn* (5 equiv)

THF, reflux, 3 h

Synthesis 2634 26452009 -, , 15 ,

10


Methyltrioxorhenium/Hydrogen Peroxide Catalytic SystemRe

The evaluation of the antioxidant and apoptogenic activity by in vivo protocols of these ligans has been evaluated.

BERNINI, R.; GUALANDI, G.; CRESTINI, C.; BARONTINI, M.; BELFIORE, M. C.; WILLFOR, S.; EKLUND, P.; SALADINO, R.

PL

MeO

HO

O

O

OMe

OH

H

H

MeO

HO

O

O

OH

OH

H

H

MeO

HO

O

O

OMe

OH

H

H

MeO

HOOH

O

OMe

OH

H

H

OH

OH

MeReO3, H2O2

CH2Cl2, MeCN

30% 30% 40%

+ +

Bioorg. Med. Chem. 5676 56822009 17 -, , 15 ,

Rhenium-Catalyzed Regioselective Alkylation of PhenolsRe

KUNINOBU, Y.; MATSUKI, T.; TAKAI, K.

MVI

OH

R1R2

OH

R1

R2cat. Re2(CO)10

J. Am. Chem. Soc. 9914 99152009 131 -, , 29 ,

Re-Catalyzed Addition of Carbonyl Compounds to the C-N Triple Bond of NitrilesRe

TAKAYA, H.; ITO, M.; MURAHASHI, S.-I.

MVI

R1

H

O

R2C NR3

cat. ReH7(PPh3)2R1 O

R2

R3

NH2

J. Am. Chem. Soc. 10824 108252009 131 -, , 31 ,

From Alkynes to Carbenes Re

F atom cis to the carbene ligand and Br cis to the NO ligand.

JIANG, Y.; BLACQUE, O.; FOX, T.; FRECH, C. M.; BERKE, H.

HJR

Br

Re

H

Ph

H

PCy3

HBF4OEt2

Cy3P NO

Cy3P

F

Br

Re

H CH2Ph

NO

PCy3 yellow solid 69%

C6H6, rt


11


Development of the First Iron Chloride-Catalyzed Hydration of Terminal AlkynesFe

WU, X.-.; BEZIER, D.; DARCEL, C.

LF

R H H2OFeCl3 (10 mol%)

DCE, 75 °C, air R

O

yields: 57 - 99%

Adv. Synth. Catal. 367 3702009 351 -, , 3 ,

A Mild and Efficient Iron-Catalyzed Synthesis of Alkenyl HalidesFe

LIU, Z.; WANG, J.; ZHAO, Y.; ZHOU, B.

LF

FeCl3*6 H2O (5 mol%)

DCM, 50 °CAr

R'

X

20 examplesyields: 48 - 98%

X = Cl, Br

R'' Ar'Ar

R'

R''

Ar'

X

Adv. Synth. Catal. 371 3742009 351 -, , 3 ,

Efficient Cross-Coupling Reactions of Nitrogen Nucleophiles with Aryl Halides in WaterFe

TEO, Y.-C.

LF

XR

FeCl3 (10 mol%)dmeda (20 mol%)

K3PO4*H2OH2O, 125 °C, 36h

NuR

up to 88%X = Br, IR = Me, OMe, F, Cl

Adv. Synth. Catal. 720 7242009 351 -, , 5 ,

13-Cis-Retinoyl Ferrocene DerivativesFe

The antiproliferative activities of ferrocenic compounds were determined in vitro using human cancer cell lines.

LONG, B.; LIANG, S.; XIN, D.; YANG, Y.; XIANG, J.

PL

COOHFe

ROH

+COO

Fe

RPPh3, DIAD

THF75-83%

Eur. J. Med. Chem. 2572 25762009 44 -, , 6 ,

12


Oxidation of Activated Methylene Groups to KetonesFe

LENZE, M.; BAUER, E. B.

PL

2-5 mol% [Fe]

t-BuOOHpyridine

O

Yield 93%TOF 3.9 h-1

[Fe] = [Fe(PHOX)2]2+[OTf]2with PHOX = phosphinooxazoline

J. Mol. Catal. A 117 1232009 309 -, , 1-2,

Artificial Metalloenzyme Catalyst For Selective Oxidation of SulfideFe

RICOUX, R.; ALLARD, M.; DUBUC, R.; DUPONT, C.; MARÉCHAL, J.-D.; MAHY, J.-P.

AE

S S

O

H2O2

Xyl A -Fe(TpCPP)

S isomerYield = 85%ee = 40%

Org. Biomol. Chem. 3208 32112009 7 -, , 16 ,

Controllable Stereoselective Three-Component Synthesis of Trisubstitued AlkenesFe

LI, H.-H.; JIN, Y.-H.; WANG, J.-Q.; TIAN, S.-K

AE

Ph Ph Ph

OH

ArH+

PhAr

Ph Ph

PhPh

Ar Ph

Tf2O/FeCl3/AgNO3 (1:1:1)

97 : 3Yield = 56%

MeNO2, 10°C, 21h+ +

Ag

Org. Biomol. Chem. 3219 32212009 7 -, , 16 ,

Preparation of Perfluoroalylthio-Substituted FerrocenesFe

Another exemples with mercury trifluoromethanethiolate [Hg(SCF3)2].

RHODE, C.; LEMKE, J.; LIEB, M.; METZLER-NOLTE, N.

GJ

FeLi

Fe

SO2(CF2)7CF3FeCF

3(CF

2)7SO

2FBuLi

hexane, TMEDA0°C, 3 h

hexane, -78°C, 10 h6%

LiHg

Synthesis 2015 20182009 -, , 12 ,

13


Synthesis of Polyhydroxyalkyl- and C-GlycosylfuransFe

10 examples, yields: 80-95%.

NAGARAPU, L.; CHARY, M.V.; SATYENDER, A.; SUPRIYA, B.; BANTU, R.

GJ

OHOH

OH

OOH

OHCH

3

O O

OEt O

O

O

OHOH

CH3

OEt

+FeCl3 (10 mol%)

4:1 EtOH-H2O, 90°C, 5 h

95%

Synthesis 2278 22822009 -, , 13 ,

Organocatalytic Kinetic Resolution of a Planar FerrocenecarbaldehydeFe

ALBA, A.-N.; GOMEZ-SAL, P.; RIOS, R.; MOYANO, A.

PL

Fe

CHO

N

N

Fe

CHO

N

N

Fe

N

N

OFe

N

N

OOH

+ +L-Proline(30 mol%)

DMSO:Acetone 5:1

at 45% conv 55%, ee 53% 24%, ee 50% 21%, ee 48%rac


Chemoenzymatic Synthesis of Optically Active 1,2-Disubstituted FerrocenesFe

MERABET-KHELLASI, M.; ARIBI-ZOUIOUECHE, L.; RIANT, O.

PL

Fe

OH

SPh

rac

Fe

SPh

(RFc)

Fe

OH

SPhOAcLipase, VA, Toluene

25°C+

(SFc)

45%, ee 90% 40%, ee 96%For CAL-B (1296U)


Co2(CO)8-Induced Domino Reactions of Ethyl Diazoacetate, CO and FerrocenyliminesFe

A separable mixture of E- and Z-isomers in ratios depending on the structure of the imine component is obtained.

BALOGH, J.; KEGL, T.; UNGVARY, F.; SKODA-FOLDES, R.

PL

EtO CHN2

O

+ CO +Fe

H

NR Fe

RN

Fe

H

O

CO2Et CONHR

CO2EtCo2(CO)8

Z and E isomers26-53%

Co

Tetrahedron Lett. 4727 47302009 50 -, , 33 ,

14


Redox Active Bifunctional Crosslinkers Fe

Cyclic voltammetry confirmed reversible one-electron redox processes of two compounds.

BERTIN, P. A.; MEADE, T. J.

PL

Fe

OMe

O

OH

Fe

OMe

O

NHBoc

Fe

HN

O

NH2

N

O

O

1) NaN3, AcOH2) PPh3

3) Boc2O, TEA

1) LiOH2) N-(2-aminoethyl)maleimide, EDC,

HOBt, TEA3) TFA

( )2

76% 72%


Ruthenium-Catalyzed C-H Bond Activation of Michael AcceptorsRu

SIMON, M.-O.; MARTINEZ, R.; GENÊT, J.-P.; DARSES, S.

LF

CONH-tBu[Ru]cat

Si(OEt)3

Si(OEt)3

CONH-tBu

[Ag]cat

PhCHOCONH-tBu

OH

Ph

Adv. Synth. Catal. 153 1572009 351 -, , 1 ,

Enantioselective Hydrogenation in Water.Ru

> 15 examples.

ZHOU, Z.; SUN, Y.

MJ

Ph

O

Ph

OH[RuCl2(p-cymene]2/L* (0.01 eq.

HCOONa (5 eq.)H2O, 40 °C, 2 h

98% ee

L*:

H3N

Ph Ph

S

O

O

HN

O

NN

2 CF3CO2

Catal. Commun. 1685 16882009 10 -, , 13 ,

A Heterogeneous Ru/CeO2 Catalyst for Transfer-allylationRu

MIURA, H.; WADA, K.; HOSOKAWA, S.; SAI, M.; KONDO, T.; INOUE, M.

LF

HO

PhMe

R

R = H, Me

Ar H

O solid Ru/CeO2catalyst

Ph Me

O

Ar

O R

up to 93% yield

170 °C, 24h

Chem. Commun. 4112 41142009 -, , 27 ,

15


Synthesis of anti-1,3-DiolsRu

ROCHE, C.; LABEEUW, O.; HADDAD, M.; AYAD, T.; GENÊT, J.-P.; RATOVELOMANANA-VIDAL, V.; PHANSAVATH, P.

LF

R1 R2

OOHRuCl3 (2 mol%), PPh3 (4 mol%)

H2 (10 bar), MeOH, 50 °C, 24 h R1 R2

OHOH

yields up to 99%de up to 98%

R1 = Pr, iPr, Ph, CH2OBn, (CH2)4OTBDPSR2 = Me, Pr, iPr, Bu, C8H17

Eur. J. Org. Chem. 3977 39862009 -, , 23 ,

Towards Long-Living Metathesis CatalystsRu

CLAVIER, H.; CAIJO, F.; BORRÉ, E.; RIX, D.; BOEDA, F.; NOLAN, S. P.; MAUDUIT, M.

LF

CO2EtEtO2C EtO2C CO2Et

N N

Ru

Cl

Cl

O NHCF3

O

0.3 mol%

Eur. J. Org. Chem. 4254 42652009 -, , 25 ,

Asymmetric αααα-Fluorination of 2-AlkylphenylacetaldehydesRu

ALTHAUS, M.; TOGNI, A.; MEZZETTI, A.

CYV

P

N N

P

Ph PhPhPh

Ru

Cl

Cl

R

H

O

H

O

R F

cat. =

SbF6

cat. (5 mol%), AgHF2 (2.4 eq)

1,2-dichloroethane, 60°C, 24h

R = Me, Et, iPr, tBu13-35% yield18-27% ee

Ag

J. Fluorine Chem. 702 7072009 130 -, , 8 ,

Alkylation and Etherification Reactions of Cinnamyl Allylic DerivativesRu

SAPORITA, M.; BOTTARI, G.; BRUNO, G.; DROMMI, D.; FARAONE, F.

PL

Cl OPh

OPh

+

+ PhOH94%, e.e. 54% (R)6%

[CpRu(N-N*)(NCMe)][PF6](3 mol%)

K2CO3 (1 equiv)

CH2Cl2, rt, 40 h

N N

N-N*

J. Mol. Catal. A 159 1652009 309 -, , 1-2,

16


Novel Hybrid Metal Complex-DNA ConjugatesRu

GHOSH, S.; PIGNOT-PAINTRAND, I.; DUMY, P.; DEFRANCQ, E.

AE

N N

N N

N N

M R

NH

O

H2NOM = Fe, Ru

Fe

Org. Biomol. Chem. 2729 27372009 7 -, , 13 ,

Supramolecular System with 3 CB[8] Locked Between Redox-Active Ru(bpy)3 ComplexesRu

ANDERSSON, S.; ZOU, D.; ZHANG, R.; SUN, S.; SUN, L.

AE

N

N

N

NN

N

N N N N

Ru2+

CB[8] CB[8]

Org. Biomol. Chem. 3605 36092009 7 -, , 17 ,

New One-Pot Synthesis of (E)-ββββ-Aryl Vinyl Halides from StyrenesRu

PAWLUC, P.; HRECZYCHO, G.; SZUDKOWSKA, J.; KUBICKI, M.; MARCINIEC, B.

CS

Ar

Me3Si

RuH(Cl)(CO)(PPh3)3Ar

SiMe3

N

O

O

X

ArX

X = I,Br80-95%yieldE/Z > 97/3

Org. Lett. 3390 33932009 11 -, , 15 ,

Ruthenium-Catalyzed Oxidation of Alcohols into AmidesRu

WATSON, A. J. A.; MAXWELL, A.C.; WILLIAMS, J.M.J.

CS

Ru cat.+R OH

H2 acceptorH2N R' N

HR'

O

R

Org. Lett. 2667 26702009 11 -, , 12 ,

17


Stereoselective Synthesis of Secondary EnamidesRu

Pratical synthetic procedures; 7 examples; addition of primary amides to alkynes.

GOOSSEN, L.J.; BLANCHOT, M.; SALIH, K.S.M.; GOOSSEN, K.

GJ

NH2

O

Ph NH

O

Ph+

94% (E/Z 1:18)(cod)Ru(met)2 (5 mol%)

Yb(Otf)3 (10 mol%)

dcypb (6 mol%)

DMF-H2O, 60°C, 6 h

Yb

Synthesis 2283 22882009 -, , 13 ,

Enantioselective Synthesis of Heteroaromatic AlcoholsRu

10 examples.

SHEN, W.Y.; LI, Y.Y.; DONG, Z.R.; GAO, J.X.

GJ

O

CH3

O

CH3 CH3

OH O

CH3

OH

CH3 CH3

O

NN

P P

Ru

H HCl

ClPh

2Ph

2

+ +*

chiral catalyst (1 mol%)

solvent

KOH (5 mol%), 40°C, 12 h

82% [ee 87% (S)]

* * (R,R)

catalyst

Synthesis 2413 24172009 -, , 14 ,

Air-Tolerant C–C Bond Formation Via Organometallic Ruthenium CatalysisRu

Substitutions of carbon pronucleophiles, cycloadditions, and addition of a diazo compound to an alkyne.

SEVERA, L.; VAVRA, J.; KOHOUTOVA, A.; CÍZKOVA, M.; SALOVA, T.; HYVL, J.; SAMAN, D.; POHL, R.;ADRIAENSSENS, L.; TEPLY, F.

PL

MeO2C

MeO2C

MeO2C

MeO2C

92%

[Cp*Ru(cod)Cl]5 mol%

DCE, airrt, 15 min

+


Ru(II)-Catalyzed Transfer Hydrogenation of Ketones and Aldehydes in AirRu

A great variety of ketones and aldehydes has been studied.

ZHAO, M.; YU, Z.; YAN, S.; LI, Y.

PL

R1 R2

O OH+

R1 R2

OH O+

cat. 1

i-PrOK / i-PrOHin air

NN

N

HN

N

Me

Me

Ru

ClPh3P

Cl

cat 1

25-99%

TOF up to 712,800 h-1


18


Cross Metathesis of ββββ-CaroteneRu

WOJTKIELEWICZ, A.; MAJ, J.; MORZYCKI, J. W.

PL

β-carotene

Hoveyda II catalyst(15 mol%)

toluene, rt, 96h, Ar

COOEt

COOEt

30%


Ring Opening-Ring Closing Metathesis of a Norbornene DerivativeRu

MONDAL, S.; YADAV, R. N.; GHOSH, S.

PL

OH

H

O

OH

HO

H

O

H

H

HHO5 mol% Grubbs'I

H2C=CH2CH2Cl2, 6h

100%

Hoveyda-Grubbs’ catalyst(30 mol%)

110°C, toluene, 2h

45%


Ruthenium Catalyst Immobilised on Polyethylene GlycolRu

The catalyst performs ring-closing metathesis of various olefins efficiently in air.

ZAMAN, S.; ABELL, A. D.

PL

Cl

O

OPEGMe

OHOPEGMe

NaH, DMF

2nd generation Grubbs' cat

CuCl, CH2Cl2

NMesMesN

RuCl

Cl

O

OPEGMe81%

67%


Ruthenium-Catalysed Transfer Hydrogenation of N-(Tert-butanesulfinyl)iminesRu

GUIJARRO, D.; PABLO, O.; YUS, M.

PL

Ar R

NS

But

O-

+

Ar R

NH2Ar = Ph, 4-MeOPh, 4-NO2PhR = Me, Et

1) [RuCl2(p-cymene)]2 cat(1S,2R)-1-amino-2-indanolt-BuOK, i-PrOH

2) HCl, MeOHYield 76-99%E.e. 95-99%


19


OsmapyridineOs

For a related synthesis of osmanaphthalene, see pp 5461-5464 in the same issue.

LIU, B.; WANG, H.; XIE, H.; ZENG, B.; CHEN, J.; TAO, J.; WEN, T. B.; CAO, Z.; XIA, H.

CY

Os

Ph3P

Ph3P

HCl Cl

PPh3, BF4

Ph

1) NC–CH3, PPh3, 81 ºC2) nBuLi

OsN

ClCl

Ph3P

Ph3PH CH3

PPh3

formal [4+2]

Angew. Chem. Int. Ed. 5430 54342009 48 -, , 30 ,

Asymmetric Catalyzed Aziridination of AlkenesCo

Variation of the substrate: 21 examples.

SUBBARAYAN, V.; RUPPEL, J. V.; ZHU, S.; PERMAN, J. A.; AND X. PETER ZHANG, X. P.

AF

+ N3SO3CH2CCl3[Co(Por*)]

C6H5Cl, 4A MS

NTces

(TcesN3) NN

NNCo

OO

OO

HNO

HNO

NHO

NHO

O O

OO[Co(Por*)] (2,6-DiMeO-ZhuPhyrin)

up to 96 % ee

Chem. Commun. 4266 42682009 -, , 28 ,

Reduction of Terphenyl Fe(II) or Co(II) Halides in the Presence of TrimethylphosphineCo

An unusual triple dehydrogenation of an alkyl group

NI, C.; ELLIS, B. D.; STICH, T. A.; FETTINGER, J. C.; LONG, G. J.; BRITT, R. D.; POWER, P. P.

MVI

MX THF FePMe3

H

Co(PMe3)

MX = CoCl, FeBr

KC8, PMe3or

Fe

Dalton Trans 5401 54052009 -, , 27 ,

Co (III) Complex Anion ReceptorCo

Synthesis, spectroscopic data and X-ray structure are described.

SINGH, A; SHARMA, R.P.; AREE, T.; VENUGOPALAN, P.

CYV

N

N

N

N

Co

O

O

O

COO

F

F

F

F

F

+

_

J. Fluorine Chem. 650 6552009 130 -, , 7 ,

20


Cobalt-Stabilized Cyclobutadiene ComplexesCo

Reaction of 11,12-didehydrodibenzo[a,e]cycloocten-5(6H)-one (strained alkyne) with cyclopentadienyl cobalt.

KORNMAYER, S.C.; ROMINGER, F;. GLEITER, R.

GJ

O

O

OCo

CpCo(CO)2

decalin, 170°C, 3 d28% (isomeric mixture)

Synthesis 2547 25522009 -, , 15 ,

Phosphine-Phosphoramidite Ligands for Asymmetric HydrogenationRh

EGGENSTEIN, M.; THOMAS, A.; THEUERKAUF, J.; FRANCIÒ, G.; LEITNER, W.

LF

R

R'R''

R

R'R''*

Rh/H2

P P

ee 99%; TOF up to 14,000h-1

N R

Ir/H2

P PNH

R

ee 97%

Me

O O

OMe

Ru/H2

P P

Me

OH O

OMe

ee 96%

P PN

P

Me

PPh2

O O

:

IrRu

Adv. Synth. Catal. 725 7322009 351 -, , 5 ,

One-Step Construction of Five Successive Rings by [2+2+2] CycloadditionRh

TANAKA, K.; FUKAWA, N.; SUDA, T.; NOGUCHI, K.

AF

O

O

Me

Me

Me

Me

O

O

O

Me

Me

+ O

Me

Me

[Rh(cod)]BF4 / (R)-segphos(10 mol %)

CH2Cl2, r.t.16 h38 %

38 % ee

Angew. Chem. Int. Ed. 5470 54732009 48 -, , 30 ,

Enantioselective Cyclization of Substituted Imidazoles via C–H Bond ActivationRh

TSAI, A. S.; WILSON, R. M.; HARADA, H.; ROBERT G. BERGMAN, R. G.; ELLMAN, J. A.

AF

53 - 98 % ee

N

NR1

R2

R3

[Rh(coe)2Cl]2 (10 mol %)(S,S',R,R')-Tangphos (19 mol %)

THF (1 M)135 - 175 °C N

NR1

R2

R3

71 - 91 %

P P

H

tBuH

tBuTangphos

10 ex.

Chem. Commun. 3910 39122009 -, , 26 ,

21


Cyclohexene-diynes and Carbon Monoxide [2 + 2 + 2 + 1] Cycloaddition ReactionRh

7 substrates used.

KALOKO, J. J.; TENG, Y.-H. G.; OJIMA, I.

AF

Me

EE

E

E

[Rh(CO)2Cl]2 (5 mol %)

+ CO60 atm DCE - TFE (10 : 1)

60 °C, 20 h

Me

EE

O

EE

85 %E = CO2Et

Chem. Commun. 4569 45712009 -, , 30 ,

Stereoselective Synthesis of syn-Configured α−α−α−α−AllenolsRh

This method was succefully applied to the total synthesis of (±)Boivinianin B

MIURA, T.; SHIMADA, M.; DEMENDOZA, P.; DEUTSCH, C.; KRAUSE, N.; MURAKAMI, M.

OS

O

MeB(OH)2

Br

Me

OHBr

.[RhCl(nbd)]2 (2.5 mol%)

KOH (0.5 equiv.)THF, rt, 3 h.

+

(Syn/anti : 99/1)86%nbd = norbornadiene

J. Org. Chem. 6050 60542009 74 -, , 16 ,

Synthesis of Cyanosporasides A and BRh

The key step is the Rh(I)-catalysed carbonylative ring-closure reaction of the allenyne

ABURANO, D.; INAGAKI, F.; TOMONAGA, S.; MUKAI, C.

OS

OSOPhSO2Ph

O

[RhCl(CO)2]2 (2.5 mol%)

CO (1 atm), toluene, 40 °C

81%

J. Org. Chem. 5590 55942009 74 -, , 15 ,

Synthesis of a Griseolic AnalogueRh

Rhodium carbenoid induced [1,2]-migration.

BHUJBAL, N.N.; KUMAR, K.S.A.; DHAVALE, D.D.

GJ

O

O O

O

O

OO

EtO

EtO

N2

O

OO

O

O

O

OEtO

EtO

Rh2(OAc)4 (2 mol%)

benzene, reflux, 15 min

67%

griseolic acid analogue

Synthesis 2423 24292009 -, , 14 ,

22


Hydrogenation of Carbocyclic and Heterocyclic Aromatic CompoundsRh

20 examples; catalysis by rhodium on graphite.

FALINI, G.; GUALANDI, A.; SAVOIA, D.

GJ

OH OH

+ +Rh/graphite (C24Rh 4% weight)

11% 3% 86%

1 atm H2, MeOH, 7 h

Synthesis 2440 24462009 -, , 14 ,

Dialdehyde Equivalents in Enantioselective Carbonyl Allylation Ir

LU, Y.; KIM, I. S.; HASSAN, A.; DEL VALLE, D. J.; KRISCHE, M. J.

AF

OH OHO O

Me Me

((S,S) > 20 : 1 d.r.)

{Ir(cod)Cl]2 (5 mol %)(R)-Cl, MeO-biphep (10 mmol %)

Cs2CO3 (40 mol %)4-Cl-3-NO2-BzOH (20 mol %)

THF (0.2 M)110 °C, 48 h

+OAc

OH OHO O

Me Me

(> 20 : 1 d.r.)

(R,S,S,R) 75 % yield> 20 : 1 d.r.

14 % mono allylation

Angew. Chem. Int. Ed. 5018 50212009 48 -, , 27 ,

Primary Allylic Alcohols Asymmetric IsomerizationIr

Variation of the ligand (10 ex.), substrate scope (10 ex. 25 - > 99 % ee).

MANTILLI, L.; GÉRARD, D.; TORCHE, S.; BERNARD, C.; MAZET, C.

AF

OH

[Ir(cod)L*]BArF4(5 ml%)

5 min H2, THFdegassed

23 °C, 22 h

O*

75 %97 % ee

P N

OL*:

Angew. Chem. Int. Ed. 5143 51472009 48 -, , 28 ,

SpiroType Ligands for Enantioselective Hydrogenation of KetiminesIr

More substrates used (> 25 ex.), 5 ligands (88 - 98 % ee).

HAN, Z.; WANG, Z.; ZHANG, X.; DING, K.

AF

N

O

PIr

+

BArF-

X

R1

R

R = H, OMe; X = CH2, O; R1 = Bn, Me, iBu

X

R1

R

+ H21 bar

[Ir] (1 mol %)

DCE10 °C, 12 h

> 99 % conv.95 - 98 % ee

[Ir]:*

Angew. Chem. Int. Ed. 5345 53492009 48 -, , 29 ,

23


Allylic Alkylation of IndolesIr

Special topic; numerous exemples; Friedel-Crafts reaction affording branched compounds (regio- & enantioselectiviy).

LIU, W.B.; HE, H.; DAI, L.X.; YOU, S.L.

GJ

O

OP N

CH3

CH3

Ph

Ph

OCO2Me

H3CO

NH

NH

H3COLigand

+

(S,Sa,S)

[Ir(cod)Cl]2 (2 mol%)

dioxane, reflux, 4 h

Ligand (4 mol%)

Cs2CO3 (100 mol%)

*

82% (ee 92%)

Synthesis 2076 20822009 -, , 12 ,

Hydrogenation of ββββ-N-Substituted and ββββ-N,N-Disubstituted Enamino EstersIr

19 examples.

HEBBACHE, H.; HANK, Z.; BRUNEAU, C.; RENAUD, J.L.

GJ

NH

CH3

O

OCH3

NH

CH3

O

OCH3

[IrCl(cod)]2 (1 mol%)

CH2Cl2, 50°C, 3 h

H2 (10 bar)

quantitative yield

Synthesis 2627 26332009 -, , 15 ,

Ir-diamine Complexes for Asymmetric HydrogenationIr

Variation of the ligand and substrate reported.

MARTINS, J. E. D.; WILLS, M.

AF

R

O

X

Ph

NH

Ph

HNR'

Ts(1 mol %)

Ir(III)Cl3 (1 mol %)

MeOH, NaOH40 °C, 24 h

+ H2

50 bar

R

OH

X

100 % conversionup to 84 % ee

Tetrahedron 5782 57862009 35 -, , 29 ,

Alkylation of 4-hydroxy Heterocycles with Alcohols Ir

GRIGG, R.; WHITNEY, S.; SRIDHARAN, V.; KEEP, A.; DERRICK, A.

AF

X

OH

O

X = O, NMe, NH

+ R OH[Cp*IrCl2]2 (2.5 mol %)

X

OH

O

R

KOH (20 mol %)N2 (1 atm)

110 °C, 48 h1 mmol

5 mmol

up to 94 %

Tetrahedron 7468 74732009 65 -, , 36 ,

24


Arynes, Alkenes, and Alkynes [2+2+2] Cycloaddition ReactionNi

QIU, Z.; XIE, Z.

AF

TMS

OTf

+ R2 + R4R3

Ni(cod)2 (5 mol %)CsF (3 equiv.)

CH3CN, r.t.

R2

R3

R4up to 78 %

R1 R1

Angew. Chem. Int. Ed. 5729 57322009 48 -, , 31 ,

Nickel/AlMe 2Cl-Catalysed Carbocyanation of Alkynes using ArylacetonitrilesNi

YADA, A.; YUKAWA, T.; NAKAO, Y.; HIYAMA, T.

MVI

Ar CN R2 R3

R2

CN

R3

Ar

cat. Ni/AlMe2Cl

R2, R3 = alkyl, aryl, silyl

Al

Chem. Commun. 3931 39332009 -, , 26 ,

Ni-catalyzed cycloaddition of Arynes and Alkenes: 9,10-DihydrophenanthrenesNi

SAITO, N.; SHIOTANI, K.; KINBARA, A.; SATO, Y.

MVI

X

X

NN

SIMes

cat. Ni(0)-SIMes

Chem. Commun. 4284 42862009 -, , 28 ,

Versatile Chemoselectivity in Ni-catalyzed Multiple Bond (Cyclo)carbonylationsNi

Reaction in CO2-expanded liquids

DEL MORAL, D.; BANET OSUNA, A. M.; CÓRDOBA, A.; MORETÓ, J. M.; VECIANA, J.; RICART, S.; VENTOSA, N.

MVI

Br

OOH

O OH

O

Ni / Fe / CO

CO2 - expanded acetone

Fe

Chem. Commun. 4723 47252009 -, , 31 ,

25


Heterocyclization by Catalytic Carbonickelation of AlkynesNi

DURANDETTI, M.; HARDOU, L.; CLÉMENT, M.; MADDALUNO, J.

MVI

I

O

R

O

XNiR

O

ER

n n n

NiBr2.bipy

Mn, DMF

E+

(n = 1, 2)

Chem. Commun. 4753 47552009 -, , 31 ,

Mechanism of Ni-Catalyzed C-O Bond Activation in Cross-Coupling of Aryl EstersNi

LI, Z. ZHANG, S.-L.; FU, Y.; GUO, Q.-X.; LIU, L.

MVI

ArO

ONi(PCy3)2

Ar'-B(OH)2Ar'-Ar (Ar'-Ac not observed)

J. Am. Chem. Soc. 8815 88232009 131 -, , 25 ,

Ni(0)-Catalyzed Formation of Azaaluminacyclopentenes via AzanickelacyclopentenesNi

A unique Nickel/Aluminum double transmetalation reaction

OHASHI, M.; KISHIZAKI, O.; IKEDA, H.; OGOSHI, S.

MVI

NR NiNR

AlMe3

[NiMe2]

AlNR

MeNi(0)

- Me-Me

Al

J. Am. Chem. Soc. 8160 81612009 131 -, , 26 ,

Ni-Catalyzed Cross-Coupling through Ni/Mg Bimetallic CooperationNi

YOSHIKAI, N.; MATSUDA, H.; NAKAMURA, E.

MVI

RX

RAr

PPh2OH

PONiP

O

MgX

cat. Ni(acac)2/PO ArMgX

Et2O, 25°C

X = F, Cl, Br, I, OCONEt2, OP(O)(OEt)2, OTf

Mg

J. Am. Chem. Soc. 9590 95992009 131 -, , 27 ,

26


K-C-T Coupling of Nonactivated Alkyl Halides with Aryl and Heteroaryl NucleophilesNi

Catalysis by a Ni pincer complex permits the coupling of functionalized grignard reagents

VECHORKIN, O.; PROUST, V.; HU, X.

MVI

K-C-TK-C-T : Kumada-Corriu-Tamao

N Ni

NMe

NMe

Cl

FG-Alkyl1-X FG-R2-MgX3 mol% cat.

TMEDA or O-TMEDA (cat.)THF, RT, 1h

FG-Alkyl1-R2-FG

sp3-sp2 coupling

51-99% yields77 examples

cat.

Mg

J. Am. Chem. Soc. 9756 97662009 131 -, , 28 ,

Nickel-Catalyzed Direct Conjugate Addition of Simple Alkenes to EnonesNi

OGOSHI, S.; HABA, T.; OHASHI, M.

MVI

O R

HH

NiR

OO H

RNi(0)

- Ni(0)

J. Am. Chem. Soc. 10350 103512009 131 -, , 30 ,

Nickel-Catalyzed Carbocyanation of Alkynes with Allyl CyanidesNi

Mechanism proposed

HIRATA, Y.; YUKAWA, T.; KASHIHARA, N.; NAKAO, Y.; H IYAMA, T.

MVI

OSiMe3

NC

HO

HO

CN

H

O1) cat. Ni/P(4-CF3-C6H4)3/AlMe3

2) Hydrolysis64%, regioselectivity = 96:4

Plaunotol

Al

J. Am. Chem. Soc. 10964 109732009 131 -, , 31 ,

Nickel-Catalyzed Ring-Opening Hydroacylation of MethylenecyclopropaneNi

Mechanism proposed

TANIGUCHI, H.; OHMURA, T.; SUGINOME, M.

MVI

HR

OR4

R2R1

R3Ni(cod)2 (5 mol%)P(n-Bu)3 (5 mol%)

toluene60-100°C

R

O

HR2

R3R4

R1

J. Am. Chem. Soc. 11298 112992009 131 -, , 32 ,

27


Ni-Catalyzed C-H Alkenylation of 1,3,4-OxadiazolesNi

MUKAI, T.; HIRANO, K.; SATOH, T.; MIURA, M.

CC

O

NN

R

R' R'

Ar O

NN

R

R'

R'O

NN

R

Me

Ar

or

Ni cat

R, R' = Alk, Ar

or+

Numerous ExamplesYields = 26 - 100%

J. Org. Chem. 6410 64132009 74 -, , 16 ,

Ni-Catalyzed AminocarbonylationNi

JO, Y.; JU, J.; CHOE, J.; SONG, K. H.; LEE, S.

CC

RN H

R'

O

Br

R"

N

O

R

R'

R"

OP

+Ni(OAc)2.4H2O, cat.

MeOM (M=K or Na),diglyme, 110°C, 10h

cat.

3R, R' = H, Alk, cycloalk, PhR" = H, Me, OMe, tBu, naphtyl Yields = 24 - 92%

J. Org. Chem. 6358 63612009 74 -, , 16 ,

Ni-Catalyzed Borylative Ring OpeningNi

CROTTI, S.; BERTOLINI, F., MACCHIA, F.; PINESCHI, M.

CC

OB

OB

O

O

NHTs

Bpin

OH NHTs

NHTs

R

OH

N

+

Ni(COD)2 (5 mol%)ligand (7.5 mol%)

K3PO4, tolueneMeOH, rt

( )n

( )nNaBO3

RCHO ( )nR = Ph, Me, Ar

( )n

Ts

n= 1, 2

Yields = 38 - 95%

Yields = 70 - 80%

Org. Lett. 3762 37652009 11 -, , 16 ,

Asymmetric HydrovinylationNi

Special topic; generation of all-carbon quaternary centersSMITH, C.R.; LIM, H.J.; ZHANG, A.; RAJANBABU, T.V.

GJ

C2H

4

OOP

N

MeMe

Ph Ph

+(1 bar)

[(allyl)NiBr]2 /L/NaBAr4 (10 mol%)

> 90% (ee 90%)

(S,Ra,S)

Ligand

CH2Cl2, -60°C, 12 h

Synthesis 2089 21002009 -, , 12 ,

28


Synthesis of Aromatic Amines, Pyrrolobenzodiazepines and PyrroloquinazolinonesNi

Microwave-assisted reduction/tandem cyclization in condensed and solid phase; 22 examples.

SHANKARAIAH, N.; MARKANDEYA, N.; ESPINOZA-MORAGA, M.; ARANCIBIA, C.; KAMAL, A.; SANTOS, L.S.

GJ

O

N3

N

CO2Me NH

N

H

O

O

90%

Ni2B (3 equiv)

MeOH-HCl (1 M)MW (70 W), 2 min

B

Synthesis 2163 21702009 -, , 13 ,

Kumada Cross-Coupling Reaction Catalyzed by Immobilized Nickel CatalystNi

15 examples, yields: 70-93%; reaction between aryl Grignard reagents and aryl halides.

CHEN, X.; WANG, L.; LIU, J.

GJ

AcO Br MgBr AcO O

OO Si NH

Ni NHCl

ClOHOHOH

+Ni cat. (2 mol%)

THF, 10°C, 12 h

74%

catalystSi

Synthesis 2408 24122009 -, , 14 ,

Synthesis of Functionalized 2-arylpyridines Ni

Scope of the reaction described.

GOSMINI, C.; BASSENE-ERNST, C.; DURANDETTI, M.

AF

XGF +

N Cl

FG'

NiBr2Bpy (10 mol %)Mn powder

TFAH

DMFN

G'F

FG

35 - 86 %

Tetrahedron 6141 61462009 65 -, , 31 ,

Diastereoselective Reductive Couplings of Aminoaldehydes and AlkynylsilanesNi

SA-EI, K.; MONTGOMERY, J.

AF

HR1

OTBS

O

+ TMS R2 + (iPr)SiH

IMes.HCl, KOt-BuNi(cod)2 R1

TBSO TMSR2

OTIPS

75 - 85 % yieldup to > 98 : 2 dr

Tetrahedron 6707 67112009 65 -, , 33 ,

29


Direct B-Alkyl Suzuki-Miyaura Cross-Coupling of Tri alkyl- boranes with Aryl BromidesPd

WANG, B.; SUN, H.-X.; SUN, Z.-.; LIN, G.-Q.

LF

R-BR'2Br

XH

FG2 mol% Pd(dppf)Cl2

Cs2CO3, THF, ref lux

R

XH

FG

31 examples55 - 99% yieldR = primary alkyls

X = COO, O, NMs, SO2NH, NFG = CHO, COCH3, CN, Cl

Adv. Synth. Catal. 415 4222009 351 -, , 3 ,

Arylamines by Pd-Catal. Addition of Arylaldehydes with Amines and Arylboronic AcidsPd

YU, A.; WU, Y.; CHENG, B.; WEI, K.; LI, J.

LF

Ar1CHO Ar2NH2 Ar3B(OH)2cat (3 mol%)

NH4Cl, SDS, H2O100 °C, 12h

HN

Ar1 Ar3

Ar2

26 examplesyield up to 96 %

Fe Pd

N

NN Cl

Adv. Synth. Catal. 767 7712009 351 -, , 5 ,

Carboaminoxylation of IndolesPd

KIRCHBERG, S.; FRÖHLICH, R.; STUDER, A.

CY

NBoc

MeO2C NBoc

MeO2C

ON

Ph

PhB(OH)2 (4 equiv), TEMPO (4 equiv)KF (4 equiv), Pd(OAc)2 (10 mol%)

propionic acid, room temp., 1 h

99%

Angew. Chem. Int. Ed. 4235 42382009 48 -, , 23 ,

Palladium-Catalyzed Di-cyanation of AcetylenesPd

ARAI, S.; SATO, T.; KOIKE, Y.; HAYASHI, M.; NISHIDA, A.

CY

HEt

PhTMSO

TMSCN (2.5 equiv), PdCl2 (5 mol%)toluene, O2 (1 atm), 100 ºC, 19 h

86% NC

H

CN

EtPh

TMSO

Angew. Chem. Int. Ed. 4528 45312009 48 -, , 25 ,

30


C-H Activation for the Preparation of IndolesPd

SHI, Z.; ZHANG, C.; LI, S.; PAN, D.; DING, S.; CUI, Y.; JIAO, N.

CY

OMe

MeO

NH2

MeO2C CO2Me+

O2 (1 atm), Pd(OAc)2 (10 mol%)N,N-Dimethylacetamide/PivOH (4:1)

120 ºC, 12 h

99%OMe

MeO

NH

CO2Me

CO2Me

Angew. Chem. Int. Ed. 4572 45762009 48 -, , 25 ,

Dihydridopalladium Complex trans-[Pd(H)2(IPr)(PCy 3)]Pd

FANTASIA, S.; EGBERT, J. D.; JURCÍK, V.; CAZIN, C. S. J.; JACOBSEN, H.; CAVALLO, L.; HEINEKEY, D. M.; NOLAN, S. P.

CY

Cy3P Pd IPr

H2 (1 atm), benzeneroom temp., 24 h

Cy3P Pd IPr

H

H

Angew. Chem. Int. Ed. 5182 51862009 48 -, , 28 ,

sp2 C–H Activation: Arylation of Enamides with Arylsil anesPd

ZHOU, H.; XU, Y.-H.; CHUNG, W.-J.; LOH, T.-P.

CY

NHAc NHAcPh

Pd(OAc)2 (10 mol%), AgF (3 equiv)dioxane, 80 ºC, 16 h

81%

Angew. Chem. Int. Ed. 5355 53572009 48 -, , 29 ,

C–H vs C–Si ActivationPd

RAUF, W.; THOMPSON, A. L.; BROWN, J. M.

BJL

XF

F

N

OCO2Bu+

+ Pd (cat) + oxidantX = SiMe3X = H

XF

F

N

O

F

F

N

O

CO2Bu

CO2Bu

60% 85%

Chem. Commun. 3874 38762009 -, , 26 ,

31


Construction of Five Contiguous StereocentersPd

HU, Y.; OUYANG, Y.; QU, Y.; HU, Q.; YAO, H.

BJL

O

N

R2

R1

n

R3C6H4X, n-Bu3NPd(OAc)2

DMF, 150 °CN

O

R1

n

R2

R3

Chem. Commun. 4575 45772009 -, , 30 ,

Sequential Coupling Involving Arenes and Ketones C–H Bond FunctionalizationPd

MAESTRI, G.; DELLA CA’, N.; CATELLANI, M.

BJL

RI

2 + R1

OH

R2

Pd(OAc)2

R

R

R2

R1O

Chem. Commun. 4892 48942009 -, , 32 ,

Regioselectivity C–H Arylation of 1,3-DimethyluracilPd

CERNOVÁ, M.; POHL, R.; HOCEK, M.

BJL

N

N

OH

HO

+ ArX + Pd(OAc)2

+ P(perFPh)3CuI, Cs2CO3

DMF, 160 °CCs2CO3

DMF, 160 °C

N

N

OAr

HO

N

N

OH

ArO

Eur. J. Org. Chem. 3698 37012009 -, , 22 ,

4-Arylation of IsoxazolesPd

FALL, Y.; REYNAUD, C.; DOUCET, H.; SANTELLI, M.

BJL

ArBr +

ON

H

H

R' PdCl2 (0.1-0.5 %)

AcOK ON

Ar

H

R'

Eur. J. Org. Chem. 4041 40502009 -, , 24 ,

32


A Second Transmetallation Step in the Negishi CouplingPd

Improvement in the Interpretation of the Mechanism of Biaryl Syntheses

LIU, Q.; LAN, Y.; LIU, J.; LI, G.; WU, Y.; LEI, A.

CJM

ClZn

O

MeO

PdPh L

L

LPd

L

Ph

ZnCl

OOMe

transmetallation

vs.

LPd

L

Ph

OOMe

Reductive elimination

ZnCl

Zn

J. Am. Chem. Soc. 10201 102102009 131 -, , 29 ,

Hyperbranched Polymers by Suzuki-Miyaura PolycondensationPd

HUANG, W.; SU, L.; BO, Z.

CJM

N(CH2)6O BO

O

Br

Br

Hyper-BranchedPolymer

Pd2dba3, PtBu3

B

J. Am. Chem. Soc. 10348 103492009 131 -, , 30 ,

Intramolecular Amination of Aromatic C-H BondsPd

MEI, T.; WANG, X.; YU, J.

CJM

RNHTf R

NTf

Pd(OAc)2 15%oxidant 2 equiv

DMF 1.25 equivDCE, 120 °C

N FTfO

additive

24 examples

J. Am. Chem. Soc. 10806 108072009 131 -, , 31 ,

Direct Intramolecular Arylation of Phenols and Anil inesPd

HUANG, C.; GEVORGYAN, V.

CJM

Br

Si X

Ph tBuSi X

Ph tBuPd(OAc)2 5 %PCy3-HBF4 10%

PivOH, Cs2CO33A MS, p-Xylene

140°CR R

X= O, NPh

Si

J. Am. Chem. Soc. 10844 108452009 131 -, , 31 ,

33


Isomerization/Polymerization of CyclopentenesPd

OKADA, T.; TAKEUCHI, D.; SHISHIDO, A.; IKEDA, T.; OSAKADA, K.

CJM

H

nN N ArAr

PdMe Cl

Pd cat

[(3,5-(CF3)2C6H3)4B]-

CH2Cl2, rt

nm

J. Am. Chem. Soc. 10852 108532009 131 -, , 31 ,

C-O and C-C Bond Reductive Elimination Pd

RACOWSKI, J. M.; DICK, A. R.; SANFORD, M. S.

CJM

NPdIV

N

O2CArO2CAr ∆

NArCO2

NBu4(O2CAr)

∆

NArCO2

NN

+

J. Am. Chem. Soc. 10974 109832009 131 -, , 31 ,

Coupling of Ammonia with Aromatic Halides and Pseudo-HalidesPd

VO, G. D.; HARTWIG, J. F.

CJM

FGX

X= I, Br, Cl, OTs

+ NH3 (5 equiv)FG

NH2

Pd[P(o-tol)3]2 < 2%CyPF-tBu2 < 2%NaOtBu 1.4 equiv

dioxane, 50-100 °C

J. Am. Chem. Soc. 11049 110612009 131 -, , 31 ,

C-H Arylation with Diaryliodonium SaltsPd

DEPREZ, N. R.; SANFORD, M. S.

CJM

N+ [PhIAr]BF4 N

Ph

Pd(OAc)2 5%

AcOH, 110 °C

J. Am. Chem. Soc. 11234 112412009 131 -, , 31 ,

34


Electrochemical Aromatic C-H Halogenation Pd

KAKIUCHI, F.; KOCHI, T.; MUTSUTANI, H.; KOBAYASHI, N.; URANO, S.; SATO, M.; NISHIYAMA, S.; TANABE, T.

CJM

NH

anode: PdX2

cathode: 2M HXaq

divided cell, (Pt)-(Pt)90 °C

X= Cl, BrNX

J. Am. Chem. Soc. 11310 113112009 131 -, , 321,

Hexacationic Dendrihos Ligands in Suzuki-Miyaura Reactions: a Dendritic EffectPd

SNELDERS, D. J. M.; VAN KOTEN, G.; GEBBINK, R. J. M. K.

CJM

P

NRMe2

NRMe2

2 Br

3

Go =

B

J. Am. Chem. Soc. 11407 114162009 131 -, , 32 ,

Enantio- and Diastereoselective CyclopropanationPd

Attack of the nucleophile to the central carbon of the π-allyl-Pd intermediateLIU, W.; CHEN, D.; ZHU, X.; WAN, X.; HOU, X.

CJM

R1NPh2

O

+

R2 OCO2Me

R3

1) [Pd(C3H5)Cl]2 L*LiHMDS, LiCl, THF

2) [O] ( removal of by-products)

Ph2N

O

R3

R2

R1

L*= FePN

O

NEt2R2O

J. Am. Chem. Soc. 8734 87352009 131 -, , 25 ,

Polymerization of Norbornene: Mechanistic AspectsPd

WALTER, M. D.; MOORHOUSE, R. A.; URBIN, S. A.; WHITE, P. S.; BROOKHART, M.

CJM

n

cat.Pd+

J. Am. Chem. Soc. 9055 90692009 131 -, , 25 ,

35


Selective Wacker Oxidation of Allylic AminesPd

WEINER, B.; BAEZA, A.; JERPHAGNON, T.; FERINGA, B. L.

CJM

R

N(Phta)R

N(Phta)CHO + R

N(Phta)

O> 99 <1

8 examples74-95% yield

PdCl2 10 mol %CuCl 1 equiv.

DMF/H2O 7:1O2, 3 days

Cu

J. Am. Chem. Soc. 9473 94742009 131 -, , 27 ,

Carboamination of AlkenesPd

ROSEWALL, C. F.; SIBBALD, P. A.; LISKIN, D. V.; MICHAEL, F. E.

CJM

R1

R1

NHCbz

+ Ar-HNCbz

Ar

R1

R1

Pd(TFA)2 10 mol%NFBS 2 equiv

BHT 1 equiv3Å MS, rt


J. Am. Chem. Soc. 9488 94892009 131 -, , 27 ,

Synthesis of Chiral Allylic BoronatesPd

LESSARD, S.; PENG, F.; HALL, D. G.

CJM

+X

OTf

BO

OH

X

BpinPd(OAc)2 5%Taniaphos 10%

PhNMe2 1.1 equiv6 examplesX= O, NBoc> 88% eeDioxane, rt

B

J. Am. Chem. Soc. 9612 96132009 131 -, , 28 ,

Oxidative Cross-Coupling Reaction MechanismPd

HULL, K. L.; SANFORD, M. S.

CJM

+ Ar-H

- AcOHPdII

L

C Ar

OAc +BQPdII

L

C Ar

BQ - Pd(0)

fastN

H NAr

+ Pd(OAc)2

J. Am. Chem. Soc. 9651 96532009 131 -, , 28 ,

36


Intermolecular Arylation of sp 3 C-H BondsPd

WASA, M.; ENGLE, K. M.; YU, J.

CJM

R2NHC6F5

O

R1H

+ ArI

Pd(OAc)2 10%JohnnPhos 20%

CsF 3 equiv.3A MS, 100 °Ctoluene

R2NHC6F5

O

R1Ar

J. Am. Chem. Soc. 9886 98872009 131 -, , 29 ,

Enantioselective αααα-Arylation of OxindolesPd

TAYLOR, A. M.; ALTMAN, R. A.; BUCHWALD, S. L.

CJM

NO

Me

+Br

TMEDA•PdMe2 4%L* 4%NaOtBu 2 equiv

cyclohexane, 50 °CN

O

Me

L*=PNMe2

tBuPh

10 examples, 63-79% yield, >94% ee

Mg

J. Am. Chem. Soc. 9900 99012009 131 -, , 28 ,

Structure of the Catalytic Species in Enantioselective Tsuji-Trost ReactionsPd

NMR, isotopic labelling and computational studies.

BUTTS, C. P.; FILALI, E.; LLOYD-JONES, G. C.; NORRBY, P.; SALE, D. A.; SCHRAMM, Y.

CJM

NH HNO O

Ph2P

Ph2P

Pd

J. Am. Chem. Soc. 9945 99572009 131 -, , 29 ,

Palladium Catalyzed Synthesis of Substituted MorpholinesPd

LEATHEN, M. L.; ROSEN, B. R.; WOLFE, J. P.

VM

O

HN

Ar

R1 Br

R2O

N

Ar

R1

R2

> 20:1 dr

Pd(OAc)2 (2 mol%)P(2-Furyl)3 (8 mol%)

NaOtBu, Toluene, 105°C

21-77% Yield

J. Org. Chem. 5107 51102009 74 -, , 14 ,

37


One-Pot Pd-Catalyzed Carboxamidation and Aldol-Type CondensationPd

CHOUHAN, G.; ALPER, H.

VM

R1

EWG

X

HN Z

OO

R2 R1

EWG

N

O

Z

OR2

Pd(0) cat.

CO, Cs2CO3

THF, 80°CZ = CHR3, NMe

40-84% Yield

J. Org. Chem. 6181 61892009 74 -, , 16 ,

Palladium (0) Mediated Generation of QuinodimethanesPd

INAGAKI, F.; MIZUTANI, M.; KURODA, N.; MUKAI, C.

VM

8-94% Yield

NH

Boc

•

EtO2CO

EWG EWG

Pd2(dba)3 (5 mol%)

Toluene, Reflux N

Boc

EWG

EWG

J. Org. Chem. 6402 64052009 74 -, , 16 ,

Palladium-Catalyzed alpha-Arylation of Tetramic AcidsPd

STORGAARD, M.; DÖRWALD, F. Z.; PESCHKE, B.; TANNER, D.

VM

N

Boc

R1

HO

O

XR2

L (4 mol%)Pd(OAc)2 (2 mol%)

K2CO3 (2.3 eq.)

THF, 80°CN

Boc

R1

HO

O

R2

60-79% Yield

i-Pri-Pr

i-Pr

P(t-Bu)2

L =

J. Org. Chem. 5032 50402009 74 -, , 14 ,

Palladium (0) Mediated Concise Entry to Furanose-Based Carbohydrate TemplatesPd

GOMEZ, A.M.; BARRIO, A.; PEDREGOSA, A.; VALVERDE, S.; LOPEZ, J. G.

VM

OO

O

O

BrNH

R1 R2

R3 B(OH)2

Pd(PPh3)4 cat.

OO

O

R3

HO N

R2

R1

10 examples60-79% Yield

J. Org. Chem. 6323 63262009 74 -, , 16 ,

38


On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type ReactionPd

LAN, Y.; DENG, L.; LIU, J.; WANG, C.; WIEST, O.;YANG, Z.; WU, Y.-D.

VM

Pd catalyzedPausand Khand Reaction

XR

CO X

R

O

DFT Study of the reaction mechanism

J. Org. Chem. 5049 50582009 74 -, , 14 ,

Palladium-Catalyzed Coupling Reactions.Pd

Synthesis of new aminophosphine complexes and their catalytic activities in the title reaction is reported.

BIRICIK, N., DURAP, F.; KEYAN, C.; GÛMGÜM, B.; GÜRBÜZ, N.; ÔZDEMR, I.; ANG, W. H.; FEI, Z.; SCOPELLITI, R.

AM

RBr+R

PdCl2L complex (1 mmol %)

Dioxane, 80 °CK2CO3 (2 eq.)

X

X = N, CH

L : NPPh2

PPh2

J. Organomet. Chem. 2693 26992009 694 -, , 16 ,

Palladium-Catalyzed in Aqueous Phase Systems.Pd

IDNESCU, A.; RUPPEL, M.; WENDT, O. F.

AM

O

OOH OH

PdPR3

CO, H2O, H+

PdPR3

H2O, H+

J. Organomet. Chem. 3806 38152009 694 -, , 18 ,

Enantioselective Pd and Rh-Catalyzed Activation of Stained RingsPd

SEISER, T.; CRAMER, N.

AE

Recent developments in the activation of strained rings, focusing on enantioselective reactions

Rh

Org. Biomol. Chem. 2835 28402009 7 -, , 14 ,

39


Pd(II)-Catalyzed Cycloisomerisation for Construction of Phosphonylated IsochromenesPd

WANG, F.; MIAO, Z.; CHEN, R.

AE

OH

HP

OMe

O

OMe

O

POMe

OOMeH

Pd(OAc)2 10 mol%

Yield = 92%

THF, 5h, rt

Org. Biomol. Chem. 2848 28502009 7 -, , 14 ,

Pd-Catalyzed Synthesis of 1-Isoindolecarboxylic Acid EstersPd

SOLÉ, D.; SERRANO, O.

AE

I

NBn

CO2Me

N

CO2Me

BnPd(PPh3)4 (0.1 eq) , K3PO4 (3 eq)

phenol, DMF, 90°C, 24h

Yield = 76%

Org. Biomol. Chem. 3382 33842009 7 -, , 16 ,

Pd-Catalyzed Cross-Coupling Reactions of Aryl ChloridesPd

RUAN, J.; SHEARER, L.; MO, J.; BASCA, J.; ZANOTTI-GEROSA, A.; HANCOCK, F.; WU, X.; XIAO, J.

AE

Cl

R

N

R

R1 R2

Ar

RR1R2NHArB(OH)2

Pd + L*

L* :MeO

OMe

PCy2Pd + L*

Org. Biomol. Chem. 3236 32422009 7 -, , 16 ,

Direct Access to Ketones from AldehydesPd

JIA, X.; ZHANG, S.; WANG, W.; LUO, F.; CHENG, J.

CS

DG

R + ArCHO

DG

R

O

ArPd(OAc)2 (10 mol%)

xylene, air, 120°C or 130°C

DG = 2-Py, -C(O)(2-Py), -O(2-Py)

Org. Lett. 3120 31232009 11 -, , 14 ,

40


Direct Alkynylation of C-H Bonds in BenzenesPd

TOBISU, M.; ANO, Y.; CHATANI, N.

CS

Pd(OAc)2 cat.MeN

OH

AgOTf

Si(i-Pr)3Br

MeN

O

Si(i-Pr)3

Org. Lett. 3250 32522009 11 -, , 15 ,

Dynamic Kinetic Asymmetric Allylation of Hydrazines and HydroxylaminesPd

The ligand 1 is the Trost bisphosphine ligand.

MANGION, I.; STROTMAN, N.; DRAHL, M.; IMBRIGLIO, J.; GUIDRY, E.

CS

R1 XNH

O

OR2

R1 XN

O

OR2

OH

1 mol% Pd2(dba)3

3-5 mol% ligand 1

X = O or N10 examplesup to 97%ee

O

Org. Lett. 3258 32602009 11 -, , 15 ,

Decarboxylative Olefination of Arene Carboxylic AcidsPd

HU, P.; KAN, J.; SU, W.; HONG, M.

CS

COOH

R1 R2

n2 equiv

+

5-10 mol% Pd(O2CCF3)2

BQ (1.2 equiv)

1-AdCOOH (4 equiv)DMSO/DMF/Dioxane

120°C, 1h

R1R2

n

n = 1, R2 = CO2Et, regioselectivity = 13:1, E/Z > 16:1n = 0, R2 = Ph or CO2tBu, 48-99% yield,n = 1, R2 = OAc, regioselectivity = 8:1 - 29:1

Org. Lett. 2341 23442009 11 -, , 11 ,

Ligand-Free Oxidative Heck ReactionsPd

SU Y.; JIAO, N.

CS

Pd(OAc)2 1-5 mol%

β-H elimination

RB(OH)2 + OAc

oxidant

OAcR

B

Org. Lett. 2980 29832009 11 -, , 14 ,

41


Enantioselective Protonation.Pd

10 examples. Critical roles of the amine salt.

HAMASHIMA, Y.; TAMURA, T.; SUZUKI, S.; SODEOKA, M.

MJ

ArHN NH

OBn

R

O O

NH

OBn

R

O O [[(R)-BINAP-Pd-OH]OTf]2 (0.05 eq.)ArNH2.HOTF (1.5 eq.)

yield up to 79%ee up to 97%

THF, RT, 24 h

Synlett 1631 16342009 -, , 10 ,

Carbonylative Cross-Coupling Reactions.Pd

15 examples.

PIREZ, C.; DHEUR, J.; SAUTHIER, M.; CASTANET, Y.; MORTREUX, A.

MJ

ArI +[B]

+ CO

(5 bar)

Pd(OAc)2/PPh3 (cat.)Na2CO3 (1.1 eq.)

THF, 80 °C Ar

O

up to 88%

B

Synlett 1745 17482009 -, , 11 ,

Stille Cross-Coupling Reactions.Pd

PATTENDEN, G.; STOKER, D. A.

MJ

X

OTf

Bu3Sn+

Pd(OAc)2 (0.1 eq.)AsPh3 (0.6 eq;)CuI (0.2 eq.)LiCl (6 eq.)

NMP, 80 °C, 24 h70%, 1:2X = OH, allyl, CH=CHCO2Et

X X

Bu

+

Sn

Synlett 1800 18022009 -, , 11 ,

Cyclization and Carbonylation.Pd

Also with primary and secondary amines instead of MeOH.

CACCHI, S.; FABRIZI, G.; FILISTI, E.

MJ

NHCOCF3

R

EtO2CO

NH

R

O

OMePd2(dba)3 (0.02 eq.)

dppf or dppb (0.05 eq.)CO (40 atm)

MeOH/THF, 80 °C, 24 h

R = H, Me, Ph

46-72%

Synlett 1817 18212009 -, , 11 ,

42


Isomerization.Pd

Influence of the substrate concentration.

MIKI, K.; SENDA, Y.; KOWADA, T.; OHE, K.

MJ

OAc

COMe

OAc

COMe

catalyst (0.05 eq.)50 °C, 7 h

Z,Z/Z,E = 79:21

Z,Z/Z,E/E,E

PtCl2, PhMe: 77:23:0PdCl2, PhMe: 3:13:84 to 0:0:100PdCl2, THF: 0:0:100PdCl2, CH2Cl2: 48:20:32Pd(PPh3)4, PhMe: 34:41:25

>99% yield with PdII

and PtII

89% yield with Pd0

Pt

Synlett 1937 19402009 -, , 12 ,

Ring-Opening Reaction of Furans.Pd

12 examples.

MIKI, K.; SENDA, Y.; KOWADA, T.; OHE, K.

MJ

OAcOAc

COR

O R

+

(1.1 eq.)

PdCl2 (0.01 eq.)PtCl2 (0.01 eq.)

PhMe, 50 °C, 7-24 h

R = H, Me, OMe,OCOMe, Ar, Bn

Pt

Synlett 1937 19402009 -, , 12 ,

Functionalization of Furan Derivatives.Pd

11 examples.

MATSUDA, S.; TAKAHASHI, M.; MONGUCHI, D. MORI, A.

MJ

OX + PhI

PdCl2(PPh3)2 (0.03 eq.)AgF (2-3 eq.)

DMSO, 100 °C, 2-3 h OPh

X = H: 41%; X = SiMe3: 53%

AgSi

Synlett 1941 19442009 -, , 12 ,

Phosphite as Ligands in Suzuki-Miyaura Cross-CouplingPd

JANG, M.; YOUNGSHIN, J.; OH, I.-K.; JUNG, H. M.; LEE, S.

PG

Ar-Br + Ar'B(OH)2

Pd(acac)2 (1 mol%)Phosphite (2 mol%)Na2CO3 (2 equiv.)

dioxane:H2O12 h, 90°C

Ar-Ar'


OP

O

OP

O O

O

t-Bu

t-Bu Met-Bu

t-Bu

Me

Phosphite :

Synthesis 2073 20752009 -, , 12 ,

43


Cross Couplings Using Potassium [1H-indol-2-yl]trifluoroboratePd

KASSIS, P.; BÉNÉTEAU, V.; MÉROUR, J.-Y.; ROUTIER, S.

PG

NBF3K

Boc

+ ArBr

PdCl2(dppf).CH2Cl2 (5 mol%)i-PrNEt2 (3 equiv.)

THF, reflux NAr

Boc


B

Synthesis 2447 24532009 -, , 14 ,

Pd-Catalyzed Cross-Coupling of Amides and Aryl Chlorides.Pd

FORS, B. P.; DOOLEWEERDT, K.; ZING, Q.; BUCHWALD, S. L.

AM

RCl H2N R'

O+

1% Pd(OAc)2, 2.2% L

tBuOH, K3PO44 mol% H2O, 110 °C

RNH

R'

OMeO P(t-Bu)2

iPriPr

iPr

OMe

L:

Tetrahedron 6576 65832009 65 -, , 33 ,

Copper-free Sonogashira Reaction of 4-Hydroxycoumarins with Alkynes.Pd

LUO, Y.; WU, J.

AM

R2+O OO

OH

OR1 R1

R2

PdCl2(PPh3)2 (10 mol%)

iPr2NEt, MeCNTsCl, 60 °C

Tetrahedron 6810 68142009 65 -, , 34 ,

Sonogashira Method in the Synthesis of Heterocyclic Compounds.Pd

Recent advances in the title application is reported.

HERAVI, M. M.; SADJADI, S.

AM

X

NHR NR

PhRcat. (PPh3)2PdCl2CuI, Et3N, DMF

+

69-82%

X = Br, IR = H, Ac, Me, Bn, Ts

Tetrahedron 7761 77752009 65 -, , 37 ,

44


Pd-Catalyzed Cross-Coupling Reaction of Halogenated 1-Phenyl pyrazol-3-oles.Pd

ARBACIAUSKIENE, E.; VILKAUSKAITE, G; ELLER, G. A.; HOLZER, W.; SACKUS, A.

AM

N N

R5 R3

R4

N N

R1

R2

N N

AcO R3

H

N N

R5 R3

R4

Pd-catalyzedcross-coupling

Pd-catalyzedcross-coupling

R1 = H, Br, IR2 = h, BrR3 = Ph, 2-ClC6H4, 2-thienyl,..R4 = H, PhR5 = Phn 2-thienyl, 3-thienyl,..

Tetrahedron 7817 78242009 65 -, , 37 ,

Chiral Amine–Imine Ligands based on trans-2,5-disubstituted pyrrolidines Pd

CHEN, H.; SWEET, J. A.; LAM, K.-C.; RHEINGOLD, A. L.; MCGRATH, D. V.

CS

Ph Ph

OAc

N

YR''

R'N

R

R

ligand

Ph Ph

CH(COOMe)2

[Pd(η3-C3H5)Cl]2

CH2(COOMe)2 11 ligands


First Synthesis of 7-Amino-5-nitroindolesPd

SANZ, R.; GUILARTE, V.; PÉREZ, A.

TJ

NH2

XO2N + R

NH

RO2N

NH

RH2N

Pd(II) 3 mol%, CuI 5 mol%Et2NH 1.5 equiv., solvent, rt

NaOH 10 equiv., 140 °C

DMA

DMF

Pd/C, 140 °C

Cu


Synthesis of Benzo[4,5]furo[3,2-c]pyridinesPd

YOON, W. S.; LEE, S. J.; KANG, S. K.; HA, D.-C.; HA, J. D.

TJ

N

O

Br R1

R2

N

O

R1

R2

Pd(OAc)2 5 mol%IPr-HCl 10 mol%

K2CO3 2 eq.DME, 130 °Csealed tube

9 examples5-95%


45


Efficient Route to 1,2-Dihydroisoquinolin-1-ylphosphonatesPd

ZHOU, H.; JIN, H.; YE, S.; HE, X.; WU, J.

TJ

15 examples42-80%

CHO

BrR1

N

PR3

R2

EtOEtO

O

R1+

R2

R3-NH2

+ HP(O)(OEt)2

Pd(II) 2 mol% Cu(II) 10 mol%

Sonogashira Cyclization-addition

THF, 4A MS, 50-60 °C

I IICu


Sequential Heck-Reduction-Cyclization ReactionsPd

IBARGUREN, O.; ZAKRI, C.; FOUQUET, E.; FELPIN, F.-X.

TJ

Pd(OAc)2 5 mol%charcoal

NO2

CO2Me

MeO2C

N2BF4

NH

O

CO2Me

+MeOH, 40 °C, 1 h

then H2 24 h 83%


IodoetherificationPd

DOROSKI, T. A; COX, M. R.; MORGAN, J. B.

TJ

R1

R2HOn

PdCl2dppf 5 mol%

NIS, toluenert

OI

R1R2

n


>20:1 dr

n = 1,2R1, R2 = H, Alk


Synthesis of Trans-ββββ-methylstyrenesPd

AL-MASUM, M.; ALAM, S.

TJ

BF3KX

Z+ ZPdCl2(dtbpf) 3 mol%

K2CO3, IPA/H2OMW , 120 °C, 30 mn

12 examples71-95 %

Z = H, Me, X, CF3, CN

B


46


Synthesis of 1-(Alkynyl)dicarbonylcyclopentadienylironPd

NAKAYA, R.; YASUDA, S.; YORIMITSU, H.; OSHIMA, K.

TJ

Fe IOC

OCFe

OCOC

R

PdCl2(PPh3)2 2.5 mol%CuI 5 mol%

+ Ramine/THF

25 °C, 30 mn

15 examples34-91%

FeCu


Cyclization Through sp3 C–H ActivationPt

YANG, S.; LI, Z.; JIAN, X.; HE, C.

CY

Ph

H

HPtCl2 (10 mol%)CuBr (2 equiv)

toluene, 120 ºC, 36 h

82%

Angew. Chem. Int. Ed. 3999 40012009 48 -, , 22 ,

Synthesis of CarbazolesPt

KONG, W.; FU, C.; MA, S.;

BJL

NR1

R2HO

R3

R4

PtCl2 (5%)

NR1

R4

R2

R3

Chem. Commun. 4572 45742009 -, , 30 ,

Metaloxetane FormationPt

WELIANGE, N. M.; SZUROMI, E.; SHARP, P.

CJM

[L2Pt(µ-OH)]nn+ + L2PtO

H

J. Am. Chem. Soc. 8736 87372009 131 -, , 25 ,

47


Asymmetric 1-4-Dihydroxylation of 1,3-Dienes Pt

BURKS, H. E.; KLIMAN, L. T.; MORKEN, J. P.

CJM

R

Pt2dba3 2.5 mol%L* 6 mol%B2(pin)2

toluene, 60 °Cthen H2O2

OHROH

L*=O

O OP

OPh

Ar Ar

Ar Ar

J. Am. Chem. Soc. 9134 91352009 131 -, , 26 ,

Synthesis of Fluorinated Platinium (II) PhosphonatesPt

BENNETT, J.A.; HOPE, E.G.; SINGH, K.; STUART, A.M.

CYV

PtO

OPh3P

Ph3PP

O

Rf

PtO

OPh3P

Ph3PP

O

Rf

RfI

Br Rf

1) Pd(PPh3)4 / Et3N / HPO(OEt)2

2) HCl (12N), 110°C3) PtCl2(PPh3)2, Ag2O

Rf = C4F9, C6F13

Rf = F, CF3, C4F9

oror

Pd

J. Fluorine Chem. 615 6202009 130 -, , 7 ,

Use of Xphos Ligand and Platinum Catalysts in The Synthesis of Vinylsilanes.Pt

HAMZE, A.; PROVOT, O.BRION, J-D.; ALAMI, M.

AM

R[Si]-H, THF Rα β

[Si]H

β-(E)-isomersexclusively 65-98%

PtO2 or PtCl2/Xphos[Si] = Et3Si, Ph2MeSi, Me2PhSi,Me2(OEt)Si, ..R = 4-CNC6H4, 4-MeO2CC6H4, 4-MeC6H4, ..

J. Organomet. Chem. 2789 27972009 694 -, , 16 ,

Synthesis of Substituted Furans and Pyrroles in Aqueous MediaPt

Feature article; 24 examples, yields: 34-96%; cyclizations of propargylic oxiranes and aziridines.

YOSHIDA, M.; AL-AMIN, M.; SHISHIDO, K.

GJ

O BuO

Bu

83%

PtCl2 (10 mol%)

2:1 dioxane-H2O, 100°C, 10 min

Synthesis 2454 24662009 -, , 14 ,

48


Platinum-Catalyzed Synthesis of Furans and PyrrolesPt

YOSHIDA, M.; AL-AMIN, M.; SHISHIDO, K.

PG

X

R1

R2 R3

XR1

R2

R3

X= O or NBn

PtCl2 (10 mol %)

dioxanne-H2O, 100°C

21 examples34-96%

Synthesis 2454 24662009 -, , 14 ,

Platinum-Catalyzed Cyclisation of bis-Phosphonate Substituted Enynes.Pt

GIBSON, S. E.; HAYCOCK, P. R.; MIYAZAKI, A.

AM

(EtO)2(O)P

(EtO)2(O)P

(EtO)2(O)P

(EtO)2(O)P4 mol% PtCl2

toluene

100%

Tetrahedron 7498 75032009 65 -, , 36 ,

Copper-Catalyzed Preparation of γγγγ-Alkylidenebutenolides and IsocoumarinsCu

INACK-NGI, S.; RAHMANI, R.; COMMEIRAS, L.; CHOURAQUI, G.; THIBONNET, J.; DUCHÊNE, A.; ABARBRI, M.;PARRAIN, J.-L.

LF

R'

I

CO2HR''

CuI, K2CO3, DMF OR''

O

R'

Adv. Synth. Catal. 779 7882009 351 -, , 5 ,

Enantioselective Copper-Catalyzed Allylic Substitution Reaction Cu

YOSHIKAI, N.; MIURA, K.; NAKAMURA, E.

LF

Ar

OP(OEt)2

O

Et2Zn Ar

Et H

OHPh2PBnN

(12 mol%)

CuCl2*2 H2O (10 mol%)

DCM, -78 °CSN2':SN2 > 94:694 - 97% ee

Adv. Synth. Catal. 1014 10182009 351 -, , 7-8,

49


Copper-Catalyzed Borylation of Aryl Halides Cu

KLEEBERGER, C.; DANG, L.; LIN, Z.; MARDER, T. B.

PG

Ar-X + B B

O

OO

OCuI (10 mol%)n-Bu3P (13 mol%)t-BuOK (1.5 equiv.)

THF, rt

B

O

OAr

19 examples92-48% yieldX = I or Br

Angew. Chem. Int. Ed. 5350 53542009 48 -, , 29 ,

Cu-Catalyzed Alkylation of Sulfonamides using AlcoholsCu

SHI, F.; TSE, M. K.; CUI, X.; GORDES, D.; MICHALIK, D.; THUROW, K.; DENG, Y.; BELLER, M.

PG

R1 S

O

O

NH2 OHR2+

Cu(OAc)2 (1 mol%)K2CO3 (4 equiv.)

neat, 150°C4 equiv.

R1 S

O

OHN R2


Angew. Chem. Int. Ed. 5912 59142009 48 -, , 32 ,

Chiral Thiophene Ligands for Copper-catalyzed Asymmetric Henry ReactionCu

BANDINI, M.; CABIDDU, S.; CADONI, E.; OLIVELLI, P.; SINISI, R.; UMANI-RONCHI, A.; USAI, M.

LF

R

O

HCH3NO2

L/Cu(OAc)2EtOH, 0 °C

R

OH

NO2

L:

NH HN

S S

TMS SMeMeS TMS

Chirality 239 2442009 21 -, , 1 ,

Asymmetric Henry Reaction Catalyzed by Bifunctional Copper-based CatalystsCu

GUO, J.; MAO, J.

LF

R

O

HCH3NO2

L/Cu(OAc)2EtOH, 0 °C

R

OH

NO2

12 chiral ligands tested

Chirality 619 6272009 21 -, , 6 ,

50


Asymmetric Copper-Catalyzed Reduction of 2-AlkenylheteroarenesCu

RUPNICKI, L.; SAXENA, A.; LAM, H. W.

PG

R

R'R

R'H

Cu(OAc)2.H2O (5 mol%)Ligand (5 mol%)PhSiH3 (1.5 equiv.)t-BuOH (2 equiv.)

toluene, 0°C to rt, 17 h

Fe PPh2P(t-Bu)2

H

MeLigand :

11 examples81-95% yield87-99% ee

Fe

J. Am. Chem. Soc. 10386 103872009 131 -, , 30 ,

Cooperative Cinchona Derivative Copper Catalyzed Asymmetric Conia-Ene ReactionCu

YANG, T.; FERRALI, A.; SLADOJEVICH, F.; CAMPBELL, L.; DIXON, D. J.

PG

R1

O O

R2 R1

O O

R2CuOTf (5 mol%)Ligand (20 mol%)

CH2Cl2, rt


N

NH

O NH

CF3

CF3

N

Ligand

J. Am. Chem. Soc. 9140 91412009 131 -, , 26 ,

Cooperative Copper/Organo Asymmetric CatalysisCu

LU, Y.; JOHNSTONE, T. C.; ARNDTSEN, B. A.

PG

N

R1

R2

R3+

CuPF6(MeCN)2 (2.5 mol%)PR3 (5 mol%)Boc-Proline (10 mol%)

CH2Cl2, 0°C, 72h

HN

R1

R2

R3


J. Am. Chem. Soc. 11284 112852009 131 -, , 32 ,

Decarboxylative Cu-Catalyzed Mannich Type ReactionCu

YIN, L.; KANAI, M.; SHIBASAKI, M.

PG

R1

NPPh2

O

R2 R3

HO2C CN+

CuOAc-(R)-DTBM-SEGPHOS ( 5 mol%)

THF, 0°C, 12h R1

HNPPh2

O

CN

R3R2

19 examples51-96% yield1.6:1 to 9.1:1 dr70-97% ee

J. Am. Chem. Soc. 9610 96112009 131 -, , 28 ,

51


Cyclopropanation CatalystsCu

11 examples. TON up to 16900

YOUSSEF, N. S.; EL-ZAHANY, E.; EL-SEIDY, A. M. A.; CASELLI, A.; CENINI, S.

PLA

O

N[M]

O

Me S

NN

[M] O

MeH

O

[M] = Cu(II), Ni(II), Co(II)

R1

R4R2

R3

cat.

EDA

R1

R2

R3

R4

CO2Et

46:54 < cis:trans < 9:91

17-97%

cat :NiCo

J. Mol. Catal. A 159 1682009 308 -, , 1-2,

New Clickable Fluorophores For Biological LabelingCu

KELE, P.; LI, X.; LINK, M.; NAGY, K.; HERNER, A.; LÖRINCZ, K.; BÉNI, S.; WOLFBEIS, O. S.

AE

N3

or

Biological target

With or without CuI

Biological target

Org. Biomol. Chem. 3486 34902009 7 -, , 17 ,

Copper(I)-Bis(Trimethylsilyl)Acetylene ComplexesCu

Theoritical study of the bonding between the Cu(I) cation and the acetylene ; 14 examples.

SREBRO, M.; MITORAJ, M.

CYV

X XCu

SiMe3SiMe3

RR1 2

1 2

X , X = O, S, NR, PR

R , R = alkyl group1

1

2

2


Ullmann and Goldberg Coupling ReactionsCu

HALDON, E.; ALVAREZ, E.; NICASIO, M.C.; PEREZ, P.J.

CYV

I

R

SH

R

S

I

R R

N

O

NH

O

N N

NNNN

N N

Cu

I

ICu

+K3PO4, cat. (5 mol%)

solvent, 110°C, 24h

8 examples, 76-99% yield

+tBuOLi, cat. (5 mol%)

dioxane, 110°C, 24h 8 examples, 70-99% yield

cat. =


52


Copper ComplexesCu

Synthesis and X-ray structures are described.

OGUADINMA, P.O.; SCHAPER, F.

CYV

Cu

N

N

L

Ph

Ph

NCL = DMAP, PPh3, Py, PMe3, MeCN,


Lithium FerrocenylenecupratesCu

BOMPAROLA, R.; DAVIES, R.P.; GRAY, T.; WHITE, A.J.P.

CYV

Cu

Li

Cu

Li[(1,1'-Fc)2Cu2Li 2(THF) 6]2 Fc + 4 tBuLi + 4 Cu(I)MesTHF

+

[(1,1'-Fc)6Cu4Li 6].2[Li(tmeda)2] was also prepared.

LiFe


Addition of Dimethylzinc to 5-(1-Arylalkylidene) Meldrum’s AcidsCu

Special topic; study of the optimized reaction conditions; 11 examples.

WILSILY, A.; LOU, T.; FILLION, E.

GJ

O O

CH2CH3

O O

CH3CH3

Ph

O O

O O

CH3CH3

PhCH3

CH2CH3

O

OP N

R

R

CH3

CH3

Me2Zn (2 equiv)

Cu(O2CCF3)2.xH2O (5 mol%)

-40°C to rt, 48 hLigand (10 mol%), DME

Ligand

R = 2-naphthyl93% (ee 76%)

Zn

Synthesis 2066 20722009 -, , 12 ,

Stereocontrolled Synthesis of 1,3-Amino AlcoholsCu

Special topic; reduction of β-sulfinylamino cyclohexanones.GONZALEZ-GOMEZ, J.C.; FOUBELO, F.; YUS, M.

GJ

O

OP N

CH3

CH3

Ph

Ph

O

Ph

NS

O

t-Bu Et2Zn

OH

Et

HN

H St-Bu

O

Ph

Ligand

(S,Sa,S)

+

CH2Cl2, -20°C, 12 h

a) Cu(OTf)2 (2,5 mol%)/L (5 mol%)

b) LiBHEt3, THF, -78°C, 3 h75%

ZnLiB

Synthesis 2083 20882009 -, , 12 ,

53


Asymmetric Ring Opening Reaction of Oxabenzonorbornadienes Cu

Special topic; desymmetrization with aluminium and Grignard reagents; numerous exemples.

MILLET, R.; GREMAUD, L.; BERNARDEZ, T.; PALAIS, L.; ALEXAKIS, A.

GJ

P N

Ph

Ph

O (CH3 )3Al

CH3

OH Ligand

+

CuTC = copper thiophene-2-carboxylate

CuTC/L (3 mol%)

MTBE, rt, 20 h

93% (anti/syn 99:1; ee 94%)

MgAl

Synthesis 2101 21122009 -, , 12 ,

Synthesis of N-Alkylated and Arylated AminesCu

50 examples; coupling of aryl chlorides with aliphatic, aromatic, and N(H)-heterocyclic amines.

SREEDHAR, B.; ARUNDHATHI, R.; REDDY, P.L.; REDDY, M.A.; KANTAM, M.L.

GJ

CH3Cl CH3

Nn-C8H17

H

NH2

+Cu-Al hydrocalcite (2.5 mol%)

DMF, 100°C, 28 h52%

Al

Synthesis 2517 25222009 -, , 15 ,

Synthesis of Macrocycles Containing Acyclic, Aromatic, and Steroidal MoietiesCu

Click chemistry.

LATYSHEV, G.V.; BARANOV, M.S.; KAZANTSEV, A.V.; AVERIN, A.D.; LUKASHEV, N.V.

GJ

O

O (CH2)8

O

O

N3

N3N NN

N NN

O OO O

(CH2)8

+

CuOTf2.0.5C6H6 (20 mol%)

toluene-DMSO, 100°C, 10 h14%

Synthesis 2605 26152009 -, , 15 ,

Polyenic Diones SynthesisCu

GAO, M.; YIN, G.; WANG, Z.; WU, Y.; GUO, C.; PAN, Y.; WU, A.

LE

Ar

O

Ar

O SMe

O

ArCuO, I2, DMSO

65°C, 20h

49-80%

Z:E = 52:48 to 88:12

Tetrahedron 6047 60492009 65 -, , 31 ,

54


Asymmetric Intramolecular Friedel-Crafts Reaction of IndolesCu

ZHOU, J.-L.; YE, M.-C.; SUN, X.-L.; TANG, Y.

LE

R1

NPG

R2O2CCO2R

2

NPG

*R2O2C

CO2R2

Cu(OTf)2 10 mol%

L* 12 mol%

t-BuOH/ PhMe

N

O

N

OO

N

L* =

80-99%62-90% ee

R1

Tetrahedron 6877 68812009 65 -, , 34 ,

Arylid-OX and Arylid-BOX derived Catalysts Applicat ions Cu

PALMA CARREIRO, E.; BURKE, A.J.; PRATES RAMALHO, J.P.; RODRIGUES, A. I.

CS

Cu(I)-ArylidBOX orCu(I)-ArylidOX

N2 CO2Et

CO2Et

H

H CO2Et

+


New Chiral Pyridine–Phosphite Ligands Cu

XIE, Y.; HUANG, H.; MO, W.; FAN, X.; SHEN, Z.; SHEN, Z.;NAN SUN, N.; HU, B.; HU, X.

CS

R1

O

R2

CuBr2 / L

Et2Zn, Et2O R1

O

R2*

up to 92%ee

L =

OO

PO

N

Zn


Enantioselective Henry Reaction Cu

RACHWALSKI, M.; STANISAW LESNIAK, S.; SZNAJDER, E.; KIELBASINSKI, P.

CS

RO

H+ MeNO2

ligand, Cu(OAc)2EtOH, rt

c.y. up to 90%R

H

OHCH2NO2

ee up to 98%

ligands :S

NR1R2HOO


55


Cu-catalyzed Asymmetric Conjugate Addition of Grignard Reagents Cu

CHEN, Y.-L.; HOPPE, D.

CS

R1

R2

OCb

Ts

1) R3MgBr cat., Cu(OTf)2 ligand

2) H+

R1

R2

OCb

TsR3 H er on C2,

up to 74.0 : 26.0dr up to 98.8:1.2

R1/R2 = Phor H, R3 = isopropenyl or allyl : Cb = CONiPr2 a typical ligand

FePCy2

MeCy2P

Mg


C-N Bond Forming Reaction Copper CatalysisCu

LAYEK, M.; RAO, A.V.; GAJARE, V.; KALITA, D.; BARANGE, D. K.; ISLAM, A.; MUKKANTI, K.; PAL, M.

TJ

NHI

BrNH

Br

R

N

R

R1

N

R

BrC-C bondreaction

C-N bondreaction

C-C bondreaction

CuI 0.1 eq.DMF, 100 °C

Sonogashira SonogashiraHeck

Suzuki 9 examples50-72%

Pd


Deprotection of Bulky (Trialkylsilyl)acetylenesAg


KIM, S.; KIM, B.; IN, J.

GJ

BzO BzO

HTIPS = i-Pr3Si TIPS

a) AgF, MeCN, rt, 3 h

b) 1N HCl, rt, 5 min 92%

Synthesis 1963 19682009 -, , 12 ,

Synthesis of αααα-Aliphatic and ββββ-Aromatic Substituted TaurinesAg


YU, H.; CAO, S.; ZHANG, L.; LIU, G.; XU, J.

GJ

SS

AgH

2N

SO3H

NH2

NH3.H

2O

AgNO3, CH

3OH

b) H2O

2, HCO

2H

a) Na2S, HCl

50%

Synthesis 2205 22092009 -, , 13 ,

56


Silver(I)-Catalyzed Asymmetric Vinylogous Mannich Reaction.Ag

The application of chiral phosphine-Schiff base type ligands in the title reaction is reported.

YUAN, Z-L.; JIANG, J-J.; SHI, M.

AM

Ar1

Ar2 OOTMS+

OO

Ar2

AgOAc (10 mol%)L6 (11 mol%)

up 81% ee, 99/1 dr10 examples

NPPh2

Cl Cl

L6

Tetrahedron 6001 60072009 65 -, , 31 ,

Cycloisomerization of 1,5-BisallenesAu

KIM, S. M.; PARK, J. H.; KANG, Y. K.; CHUNG, Y. K.

CY

NPh NPh

Au(IPr)Cl (10 mol%)AgBF4 (10 mol%)

toluene, 75 ºC, 30 min.

93%

Angew. Chem. Int. Ed. 4532 45352009 48 -, , 25 ,

Cycloaromatization of 2,4-Dien-6-yne Carboxylic AcidsAu

GARCÍA-GARCÍA, P.; FERNÁNDEZ-RODRÍGUEZ, M. A.; AGUILAR, E.

CY

MeO

CO2H

F3C

AuClP(p-CF3C6H4)3 (5 mol%)AgSbF6 (15 mol%), CH2Cl2, reflux

45%

F3C

MeO

Angew. Chem. Int. Ed. 5534 55372009 48 -, , 30 ,

Gold-Catalyzed Oxidative Dimerization of Propargylic AcetatesAu

CUI, L.; ZHANG, G.; ZHANG, L.

PL

R

OAc

R'

RR'

O

R

R

O

(2-biphenyl)Cy2PAuNTf2 (5 mol%)selectfluor (2 equiv)

MeCN:H2O = 500:160°C, 25-40 min

Bioorg. Med. Chem. Lett. 3884 38872009 19 -, , 14 ,

57


Vinyl Substituted Triazoles by Au(I) Catalyzed Alkyne ActivationAu

DUAN, H.; YAN, W.; SENGUPTA, S.; SHI, X.

PL

NH

N

N

N

N

N

R3

R4

H

R4R3PPh3AuOTf

Toluene, 80°C+

R3 = p-MePh, p-F-Ph, n-Bu, Ph, TMSR4 = H, Ph, n-Pr, Me

70-96%

Bioorg. Med. Chem. Lett. 3899 39022009 19 -, , 14 ,

Unusual Rearrangement.Au

14 examples.

XIAO, H.-Q.; SHU, X.-Z.; JI, K.-G.; QI, C.-Z.; LIANG, Y.-M.

MJ

OHO Ph

Ph

NaAuCl4.2H2O (0.02 eq.)

PhH, 50 °C, 5 h Ph

O O

PhPh

O

+( )4

58% 35%

Catal. Commun. 1824 18272009 10 -, , 14 ,

Water-Soluble (Phosphane)gold(I) Complexes - Applications as Recyclable CatalystAu

ELIE, B. T.; LEVINE, C.; UBARRETXENA-BELANDIA, I.; VARELA-RAMÍREZ, A.; AGUILERA, R. J.; OVALLE, R.; CONTEL,M.

LF

Au

Cl

PR

SO3Na

SO3NaAu

Cl

PR

R

SO3Na

R = Bu, Cp R = Bu, Cp

Recyclable catalyst Cytotoxic

Eur. J. Inorg. Chem. 3421 34302009 -, , 23 ,

Monomeric Alkyne ComplexesAu

DIAS, H. V. R.; FLORES, J. A.; WU, J.; KROLL, P.

CJM

N

M

N

N

Ar Ar

C3F7C3F7

RR

AgCu

J. Am. Chem. Soc. 11249 112552009 131 -, , 31 ,

58

Bibliographic Notebooks For Organometallic Chemistry2009, 27, ( 6)

Enantioselective Ring-Expansion of CylopropanolsAu

KLEINBECK, F.; TOSTE, F. D.

CJM

OH

•

RAu* cat 2.5 mol%NaBARF 5 mol%

DCE, -30 °C

O

R

MeOMeO

PAr2-AuClPAr2-AuCl

Au*=

13 examples, > 84% ee

J. Am. Chem. Soc. 9178 91792009 131 -, , 26 ,

Organo and Transition Metal Catalysis RelayAu

HAN, Z.; XIAO, H.; CHEN, X.; GONG, L.

CJM

+R2

NH2

NH

CO2EtEtO2C

Ph3PAuMe 5 mol%

Chiral Bronsted acid 15mol%

Toluene, rt

R2

NH

R1

16 examples87-98% ee

R1

J. Am. Chem. Soc. 9182 91832009 131 -, , 26 ,

Furannulation.Au

12 examples.

PRAVEEN, C.; KIRUTHIGA, P.; PERUMAL, P. T.

MJ

OHR AuBr3 (0.05 eq.)

ClCH2CH2Cl2, 25-60 °C( )n n = 1, 2, 3

( )n

O

60-92%

Synlett 1990 19962009 -, , 12 ,

A Palladium-Catalyzed Synthesis of Isatins(1H-Indole-2,3-diones).Au

A Palladium-Catalyzed Synthesis of Isatins(1H-Indole-2,3-diones) from Haloethynylnitro-benzenes is reported.SODERBERG, B. C. G.; GORUGANTULA, S. P.; HOWERTON, C. R.; PETERSEN, J. L.; DANTALE, S. W.

AM

NO2

I

R RNH

O

OPdCl2(PPh3)2

acetone 47-70%

Ag

Tetrahedron 7257 73632009 65 -, , 36 ,

59


Intramolecular Hydroamination of αααα-Amino AllenamidesAu

MANZO, A. M.; PERBONI, A. D.; BROGGINI, G.; RIGAMONTI, M.

TJ

R'NH

RO

MeN

•

N

R'

R

O

Me N

R'

R

O

Me+

AuCl3 5 mol%

MeCN, reflux

cis22-65%

trans4-12%

6 examplesR = Alk, Ph, Bn;

R' = Boc, Bn


Total Spontaneous ResolutionZn

LENNARTSON, A.; HAKANSSON, M.

HJ

Λ-five coordinate complex ∆-five coordinate complexfast

Λ-crystals

slow spontaneous resolution

[Zn(S2CNEt2)2(vinim)] (vinim=1-vinylimidazole)[Cd(S2CNEt2)2(lut)] (lut=2,6-lutidine)

Cd

Angew. Chem. Int. Ed. 5869 58712009 48 -, , 32 ,

Base Stabilised Dizinc DicationZn

SCHULZ, S.; SCHUCHMANN, D.; KROSSING, I.; HIMMEL, D.; BLÄSER, D. AND BOESE R.

HJ

Zn

Zndmap

dmapSingle crystals

H(OEt2)2][Al{OC(CF3)3}4]+ 2-2Cp*H

[Zn2(dmap)6][Al{OC(CF3)3}4]2

Al

Angew. Chem. Int. Ed. 5748 57512009 48 -, , 31 ,

Structurally Defined Potassium-Mediated ZincationZn

CLEGG, W.; CONWAY, B.; GRAHAM, D. V.; HEVIA, E.; KENNEDY, A. R.; MULVEY, R. E.; RUSSO, L; WRIGHT, D. S.

HJ

N

N

N

K

N

Zn

R1

R1 = Et, nBu

R1 +

N

R2

R2= H, Et, iPr, tBu, Ph

N

R2 Zn

Zn

N

R2

R1 R1

R1 R1

N

N NK

N

NNK

hexane

or hexane/THFSeven of the zincated intermediate complexes have

been isolated and characterised

K

Chem. Eur. J. 7074 70822009 15 -, , 29 ,

60


Polyfunctional Arylmagnesium, Arylzinc and Benzylic Zinc ReagentsZn

PILLER, F. M.; METZGER, A.; SCHADE, M. A.; HAAG, B. A.; GAVRYUSHIN, A.; KNOCHEL, P.

HJ

OBocZn, LiCl, THF, 25°C,14 h

OBoc

Br

OBoc

Br

1.

2. [Pd(dba)2](2 mol%), tfp (4 mol%), 25°C, 12h

Mg, LiCl, THF, -20°C, 1h1.

2. [Pd(dba)2](2 mol%), tfp (4 mol%), 25°C, 3h

91% yield

97% yield

Br

CF3

I CF3

Br

I CO2Et

60% yield

CO2Et

MgLiPd

Chem. Eur. J. 7192 72022009 15 -, , 29 ,

Multinuclear Magnesium, Calcium and Zinc ComplexesZn

All complexes have been structurally characterized by X-ray diffraction.

PIESIK, D. F.-J.; STADLER, R.; RANGE, S.; HARDER, S.

HJ

N NHO tBu

tBu

tBu

tBu

OH

LH2

2 Mg[N(SiMe3)2]2.(THF)2 L[MgN(SiMe3)2.THF]2

2 Ca[N(SiMe3)2]2.(THF)2 [LCa.THF2]2

2 Zn[N(SiMe3)2]2[LZn]3

MgCaSi

Eur. J. Inorg. Chem. 3569 35762009 -, , 24 ,

Asymmetric Addition of Terminal Alkynes to N-(Diphenylphosphinoyl)imines Zn

YAN, W.; MAO, B.; ZHU, S.; JIANG, X.; LIU, Z.; WANG, R.

OC

N

R1

P

O

Ph

Ph

R2+N

OHL* :

CH2Cl2, 0 °C

Et2Zn, L* HN

R1

P

O

Ph

Ph

R2

ee up to 96%

Eur. J. Org. Chem. 3790 37942009 -, , 22 ,

Stereogenic-at-Metal Zn- and Al-Based N-Heterocyclic Carbene (NHC) ComplexesZn

X-ray of Zn complex is described

LEE, Y.; LI, B.; HOVEYDA, A. H.

MVI

R1

R2 OPO(OEt)2

NMesN

ZnSO

O

O Me

Ph Ph

OR2

alkyl R1

5-10 mol%

(alkyl)2Zn, no Cu salt

>98:<2 SN2':SN2up to 97.5:2.5 er

J. Am. Chem. Soc. 11625 116332009 131 -, , 32 ,

61


Cyclodextrin-Dimer Based Supramolecular Assembly as Ester Hydrolysis CatalystZn

X = H : Higher catalytic activity

ZHOU, Y.-H.; ZHAO, M.; SUN, H.; MAO, Z.-W.; JI, L.-N.

PLA

X X

CD CD

Guest : CD (cyclodextrin) dimer Host

tBuN

NH2Zn

NH2 OH2

OH2

NO2MeO2C

Substrate = pNA

Host-Guest supramolecular system = ester hydrolysis catalyst

X = H, N

J. Mol. Catal. A 61 672009 308 -, , 1-2,

1,2,4-Oxadiazole SynthesisZn

AUGUSTINE, J. K.; AKABOTE, V.; HEGDE, S. G.; ALAGARSAMY, P.

LE

N

R1

N

R2H2N

HO

+PTSA-ZnCl2

DMF, 80°C

NO

NR1 R2

77-95%

J. Org. Chem. 5640 56432009 74 -, , 15 ,

Vinylogous Mannich ReactionZn

Different regio- and stereoselectivities are observed when using silver salts

GU, C.-L.; LIU, L.; WANG, D.; CHEN, Y.-J.

LE

O O

OTMS RO2C

N

H

SO

+Zn(OTf)2

O O

O

NH

RO2C

SO

50-86%up to 95:05 dr

Ag

J. Org. Chem. 5754 57572009 74 -, , 15 ,

Regio- and Chemoselective Multiple Functionalization of Chloropyrazine DerivativesZn

MOSRIN, BRESSER, M. T.; KNOCHEL, P.

CS

N

N

Cl

Cl1) TMPZnCl.LiCl 25°C, 30 min.

2) Ethyl 4-iodo-benzoate, [Pd] N

N

Cl

Cl

EtO2C80%

1) TMPZnCl.LiCl 25°C, 30 min.

2) CuCN. LiCl3) PhCOCl N

N

Cl

Cl

EtO2C90%

O

Ph

CuPd

Org. Lett. 3406 34092009 11 -, , 15 ,

62


Tetranuclear Zinc Cluster for Chemoselective Acetylation of AlcoholsZn

IWASAKI, T.; MAEGAWA, Y.; HAYASHI, Y.; OHSHIMA, T.; MASHIMA, K.

OS

OH

O2N

OAc

O2N

>99%

Zn4(OCOCF3)6O (1.25 mol%)

EtOAc, 18 h., reflux

Synlett 1659 16632009 -, , 10 ,

Nucleophilic Ring Opening of Mono-Activated cyclopropanesZn

The method generate useful γ-arylselenenyl ketones, acids, aldehydes in moderate to good yieldsNAZARI, M.; MOVASSAGH, B.

OS

Se Se Se Zn

Se COMeCOMeZn/AlCl3

CH3CN, 70 °C, 1 h. 2

70 °C, 5 h. 87%

Al

Synlett 1803 18052009 -, , 11 ,

Amino Thiols versus Amino Alcohols in the Asymmetric Catalysis Zn

SUBIRATS, S.; JIMENO, C.; PERICÀS, M. A.

CS

Ph3COPh

NX

ZnCH3

ZnH3C

R

HO

HHO

R (R)X = S, O


Synthesis of Adamantyl-Containing αααα-AminophosphonatesCd

6 examples, yields: 68-82%; solvent-free, multicomponent reaction.

KABACHNIK, M.M.; MINAEVA, L.I.; BELETSKAYA, I.P.

GJ

NH2

NH

P(O)(OEt)2

CH3

CH3

i-PrCHO(EtO)2P(O)H+ +

MW, molecular sieves, 20 min

CdI2 (1 mol%)

72%

Synthesis 2357 23602009 -, , 14 ,

63


Hg(OTf) 2-catalyzed CyclizationHg

NAMBA, K.; KAIHARA, Y.; YAMAMOTO, H.; IMAGAWA, H.; TANINO, K.; WILLIAMS, R. M.; NISHIZAWA, M.

HJ

O

TsHN

HO

OH

Hg(OTf)2 (2 mol%)

CH3NO2, r.t., 20 min NNH

H

OH

O

Ts

84% yield

Towards Palau’amine

Chem. Eur. J. 6560 65632009 15 -, , 27 ,

Synthesis of Dipeptidyl Boronate DerivativesB

42 examples; tested [as B(OH)2 form obtained after hydrolysis] as proteasome inhibitors.

ZHU, Y.; ZHAO, X.; ZHU, X.; WU, G.; LI, Y.; MA, Y.; YUAN, Y.; YANG, J.; HU, Y.; AI, L.; GAO, Q.

GJ

NH2

B NH

NH

N

N

O

O

Ph

BCl

2CHB(OCH

3)2

J. Med. Chem. 4192 41992009 52 -, , 14 ,

Nickel/AlMe 2Cl-catalysed Carbocyanation of Alkynes Using ArylacetonitrilesAl

YADA, A.; YUKAWA, T.; NAKAO, Y.; HIYAMA, T.

LF

Ar CN

R R'

cat. Ni/AlMe2Cl CN

R R'

Ar

Ni

Chem. Commun. 3931 39332009 -, , 26 ,

1,1’-Disubstituted Ferrocenes with AluminumAl

WRACKMEYER, B.; KLIMKINA, E. V.; MILIUS, W.

HJ

FeLi

LiTMEDA Fe

Fe

Fe

Al

Al

py

py py=pyridine

1. RAlCl22. py, THF

-LiCl

R=Me, Et

Li

Eur. J. Inorg. Chem. 3155 31622009 -, , 21 ,

64


Aluminum Complexes with Bidentate N,N-Dialkylaniline–arylamido LigandsAl

All complexes are efficient catalysts for the ring-opening polymerization of ε-caprolactone.GAO, A.; MU, Y.; ZHANG, J.; YAO, W.

HJ

NH

N

R2 R2

R3

R1 R1

N

N

R2 R2

R3

Al

R1 R1

AlMe3

8 examples fully characterised

Eur. J. Inorg. Chem. 3613 36212009 -, , 24 ,

A Stable Carbene Adduct of DibromosilyleneSi

Short Si-C bond due to the donation of the carbene carbone lone pair into the vacant Si p orbital

FILIPPOU, A.C.; CHERNOV, O.; SCHNAKENBURG, G.

EJ

SiBr4 KC8

THFN

N

R

R

N

N

R

R

SiBr3

N

N

R

R

hexanert

SiBr2

..

+

Br-

48%

R = 2,6-iPr2C6H3

_

K

Angew. Chem. Int. Ed. 5687 56902009 48 -, , 31 ,

Dichlorosilylene Stabilized by a Lewis BaseSi

First base stabilized SiCl2 stable at room temperature

GHADWAL, R.S.; ROESKY, H.W.; MERKEL, S.; HENN, J.; STALKE, D.

EJ

..SiCl4 KC8

N

N

R

R

N

N

R

R

N

N

R

R

hexanert

tolueneSiCl4 SiCl2

R = 2,6-iPr2C6H3, 48%

R = 2,4,6-Me3C6H2, 28%

K

Angew. Chem. Int. Ed. 5683 56862009 48 -, , 31 ,

Effect of the Central Atom on the Size of Group 14 TetratolylsSi

Such compounds are interesting due to the ease of the functionalisation at the Me group of Tol

NG, M.C.C., CRAIG, D.J.; HARPER, J.B.; VAN-EIJCK, L.; STRIDE, J.A.

EJ

E(Tol)4(E = Si, Ge, Sn, Pb) (Tol)3GeGe(Tol)3

GeSnPb

Chem. Eur. J. 6569 65722009 15 -, , 27 ,

65


New N-Aryl Heterocyclic SilylenesSi

Silylenes can be complexed on Ni(COD)

KONG, L.; ZHANG, J.; SONG, H.; CUI, C.

EJ

NSi

N

R

R

NSiCl2

N

R

R

N

N

R

R

SiCl3

SiCl3

R = MesKC8/THF KC8/THF

R = 2,4,6-iPr3C6H2-78°C -78°Ca b

a,

b,

43%

61%

KNi

Dalton Trans 5444 54462009 -, , 28 ,

A Phosphonium Sila-Ylide Reacting as a Sila-Wittig ReagentSi

Silene 1 is complexed by O

GAU, D.; KATO, T.; SAFFON-MERCERON, N.; COSSIO, F.P.; BACEIREDO, A.

EJ

NDipp

SiCl2PhR2PPhR2P

NDipp

Si

Mg/THF

rtNiPr2

PiPr2N

MesCHO

Et2O/rtNDipp

Si CHMes

PhR2P

O 1

Dipp = 2,6-iPr2C6H3

R2P = 61%

2 diastereoisomers 85/15

+ -

Mg

J. Am. Chem. Soc. 8762 87632009 131 -, , 25 ,

A Trisilacyclopentadienyl Ligand for Transition Met al ComplexesSi

YASUDA, H.; LEE, V. YA.; SEKIGUCHI, A.

EJ

SiSi

Si

Et Et

R

R

R R = SiMetBu2

Li

Rh(CO)2acac SiSi

Si

Et Et

R

R

R

Rh(CO)2

SiSi

Si

Et Et

R

R

R

RuCp* .THF

toluene/1h/rt

1/4(Cp*RuCl)4

THF/Et2O/rt/1h

LiRuRh

J. Am. Chem. Soc. 9902 99032009 131 -, , 29 ,

DFT Calculations about Insertion of Silylenes into the Si-Cl BondSi

Key step: interaction between Si lone pair orbital and sigma(Si-Y) orbital at the transition state

LAI, G.; XU, Z.; JIANG, J.; KIRA, M.; QIU, H.

EJ

Me2SiYR2SiCl

Me2Si SiR2Y

Cl

R = H, Me Y = H, F, Cl, Me, SiH3


66


Push-Pull >E=P- Compounds (E = Si, Ge) and their Anion RadicalsSi

One-electron reduction of 1 with KC8 gave persistent phosphasilene and phosphagermene anion radicals

LEE, V. YA.; KAWAI, M.; SEKIGUCHI, A.; RANAIVONJATOVO, H.; ESCUDIE, J.

EJ

ER R

R'R'

R = SiMetBu2

R' = SiMe3Li/THF

R2ELi2Mes*PCl2

R2E=PMes*THF/rt/1h Mes* = 2,4,6-tBu3C6H21

E = Si, 34%; Ge, 40%

GeLiK


A Silyl(silylene)ruthenium ComplexSi

Very unusual cleavage of 3 Si-C bonds at rt with replacement by alcoxy groups

HASHIMOTO, H.; SATO, J.; TOBITA, H.

EJ

Cp*Ru(CO)(py)Me

HSiMe2SiMes2Me

Cp*(CO)Ru=SiMes2

SiMe3

ROH/rt

RNC/C6D6

Cp*(CO)Ru CNR'

Si(OR)3

(R' = tBu, Xyl)(R = Me, Et)

(py = pyridine)

rt/2d/toluene75% 65-99%

Ru


Sila- and GermaplatinacyclesSi

Mechanism of formation of 1 is given. With Si instead of Ge, (Ph2PCH2CH2PPh2)(SiHAr2)2 is obtained in 56%

BRADDOCK-WILKING, J.; BANDROWSKI, T.; PRAINGAM, N.; RATH, N.P.

EJ

PPtMe2

PPh2

Ph2

PPt

P Ge

Ge

GeAr2

GeAr2

Ph2

Ph2

Ar2

Ar2

H2GeAr2/C7D8

GeH H

H2GeAr2 =

150°C/3h

55%

GePt


Iron Complexes with Different Group 14 Element LigandsSi

Replacement of Et3Si (E = Si in 1) by Et3Ge or Et3Sn using Et3GeH or Et3SnH is easy

ITAZAKI, M.; KAMITANI, M.; UEDA, K.; NAKAZAWA, H.

EJ

Cp(CO)(py)FeSnEt3

(py = pyridine)

Et3EH

rtEt3E Fe SnEt3

H CO

Cp E = Si, 58%Ge, 81%

Sn, 87%1

GeSnFe


67


Silylenes and Germylene Complexes of RutheniumSi

TAKAOKA, A.; MENDIRATTA, A.; PETERS, J.C.

EJ

H2MRR'

Ph2P

Ph2P

PPh

Ru

Si Ph2P

Ph2P

PPh2

Ru

Si

HMRR'

,

THF/-78°C

M = Si; R, R' = Ph, 91%

R = Ph, R' = Me, 95%

M = Ge; R, R' = Ph, 74%

GeRu


Silylene Transfer to Keto EstersSi

The reaction involves transfer of tBu2Si. Gamma lactones can also be obtained by such a process

HOWARD, B.E.; WOERPEL, K.A.

EJ

R

O

O

O Ph

R

OH COOH

Ph

SiMe

Me

tBu

tBu R = Me, Et, Ph, iPr, tBuAgOTs (10% vol)/ -25°C

1)

2) HF.pyridine

47-84%

Ag

Tetrahedron 6447 64532009 65 -, , 33 ,

Cationic Crown Ether Complexes of Ge(II)Ge

[12]crown 4 sandwiching a Ge(II) dication has also been obtained

RUPAR, P.A.; BANDYOPADHYAY, R.; COOPER, B.F.T.; STINCHCOMBE, M. R. RAGOGNA, P.J.; MACDONALD, C.L.B.;BAINES, K.M.

EJ

O

Ge

Cl

O O

OO

GeCl3

GeCl2. dioxane1/2 crown 5[15]

Angew. Chem. Int. Ed. 5155 51582009 48 -, , 28 ,

Ge(II) Dications Stabilized by Crown Ethers and AzamacrocyclesGe

First halide free dicationic Ge(II) species with N (or O) donor macrocycles

CHENG, F.; HECTOR, A.L.; LEVASON, W.; REID, G.; WEBSTER, M.; ZHANG, W.

EJ

GeCl2. dioxane

Me4-cyclam

CH2Cl2/rtGe

N

N

NN

2+

2[GeCl3]-

95%

Angew. Chem. Int. Ed. 5152 51542009 48 -, , 28 ,

68


A Stable o-Quinodimethane and the Corresponding EndoperoxideGe

Endoperoxide 2 is obtained from o-quinodimethane 1 with triplet oxygen, without activation

GHEREG, D.; ECH-CHERIF EL KETTANI, S.; LAZRAQ, M.; RANAIVONJATOVO, H.; SCHOELLER, W.W.; ESCUDIE, J.;GORNITZKA, H.

EJ

Mes2Ge=CR2

Et2O

O

O

CR2

GeMes2O

O GeMes2

CR2

CR2

GeMes2O

O GeMes2

CR2

OOEt2O

- 80°C

1, 38%

2, 36%

3O2

1 2

Chem. Commun. 4821 48232009 -, , 32 ,

Neutral and Cationic Ge(II)Pyrazolyl CompoundsGe

DFT calculations have been performed on energetic aspects of different isomers

KRUMMENACHER, I.; FERNANDEZ, I.; RÜEGGER, H.; WEIGEND, F.; BREHER, F.

EJ

Ge[N(SiMe3)2]2

N

N

R

R' Ge

Ge

N

N

R

R'

N

N

R

R'

N

N

R

R'

hexane, rt

H(3,5-RR'pz)pz = pyrazole

R = R' = CF3, 74%

R = CF3, R' = Me, 77%

Si

Dalton Trans 5335 53472009 -, , 27 ,

DFT Calculations on Aluminum ChlorogermylenoidGe

Donating electron of a Cl atom of AlCl3 to unoccupied p-orbital of Ge.

LI, W.-Z.; CHENG, J.-B.; LI, Q.-Z.; GONG, B.-A.; SUN, J.-Z.

EJ

Al

Cl

Cl

GeH

HCl

H2GeClAlCl2 has 3 equilibrium structures in gas phase

and in solution in C6H12, THF, DMSO, H2O.

This one is the predominent form.

Al

J. Organomet. Chem. 2898 29012009 694 -, , 18 ,

Hypervalent Organobismuth(III) Chlorides and their Germylpropionate DerivativesGe

In vitro antiproliferative activity of 1 on gastric carcinom cells much higher than cis platin (R = Ph, Cy)

ZHANG, X.-W.; XIA, J.; YAN, H.-W.; LUO, S.-L.; YIN, S.-F.; AU, C.-T.; WONG, W.-Y.

EJ

Br

Br

N

Bi

R

Cl

N

Bi

R

OC(O)CH2CH2GePh3

NaOH/H2O

1) RNH2/Et3N/DMF

2) BuLi/Et2O

3) BiCl3/Et2O/-78°C

93-94%

87-92%

HOC(O)CH2CH2GePh3

1

BiLiNa

J. Organomet. Chem. 3019 30262009 694 -, , 18 ,

69


Germylene and Stannylene as Strong Donor LigandsGe

Germylene and stannylenes R2E are strong donor ligands

PORTNYAGIN, I.A.; NECHAEV, M.S.

EJ

R2EM(CO)5THF

R2E M(CO)5

R = OCH2CH2NMe2

E = Ge, Sn

Fe2(CO)9

THFR2E Fe(CO)4

M = Cr, Mo, W2h/THF

20-71%E = Ge, 61%

Sn, 73%

SnCrMoWFe

J. Organomet. Chem. 3149 31532009 694 -, , 19 ,

DFT Calculations on GermaallenesGe

2 and 3 have more stable cyclic structures; 4 has a linear allenic type structure

SK, M.A.; XI, H.-W.; LIM, K.H.

EJ

H2Ge=C=CH2 H2C=Ge=CH2H2Ge=Ge=CH2 H2Ge=C=GeH2 H2Ge=Ge=GeH2

1 2 53 4


Stable LGe(II)R Compounds Obtained by Addition ReactionsGe

LGe(II)R compounds can also be obtained by addition of RH to 2. AgOTf is used to obtain 1JANA, A.; NEKOUEISHAHRAKI, B.; ROESKY, H.W.; SCHULZKE, C.

EJ

NGe

N

Ar

OTf

Ar

NGe

N

Ar

OH

Ar

NGe

N

Ar

Ar

toluene, H2O

rt

NtButBuN

toluene, rt82%

2, 90%1

Ag


Reaction of Vinyltributylgermanes with Aryl HalidesGe

The reaction occur under Heck conditions

TORRES, N.M.; LAVIS, J.M.; MALECZKA JR, R.E.

EJ

Bu3GeOH OH

PhPd(OAc)2, PPh3

Bu4NBr or Bu4NHSO4

(Ar = C6H5, tolyl, X = Br, I)

base: K2CO3, NaHCO3, Ag2CO3

2 equiv ArX/16h

0 to 65%

depending experimental

conditions

NakPdAg


70


New Organostannoxanes with Fluorescent LigandsSn

1, the X-ray structure of which is reported, exhibits an enhanced two-photon absorption compared to LCOOH.

LI, D.; HU, R.; ZHOU, W.; SUN, P.; KAN, Y;; TIAN, Y.; ZHOU, H.; WU, J.; TAO, X.; JIANG, M.

TT

Sn OSn

OSn

Sn

O

LO

O

OO

L

OO

LOL

R

R

R

R

R R

R R

N

S

R = nBu

R2SnO + LCOOH

benzene reflux

- H2O

= L1

Eur. J. Inorg. Chem. 2664 26722009 -, , 18 ,

A DFT Study of Vicinal 119Sn-13C and 119Sn-1H Spin-Spin Couplings in Organotin(IV)Derivatives

Sn

CASELLA, G.; FERRANTE, F.; SAIELLI, G.

LGE

R3Sn

R' R''

R'''

φ3J(119Sn,13C) = f(φ)

3J(119Sn,1H) = f(φ)

The Karplus-type dependence on the dihedral angle of vicinal spin-spin couplings involving 119Sn in organotin(IV) derivatives has been studied by DFT calculations

Eur. J. Org. Chem. 3526 35342009 -, , 21 ,

Synthesis of 1,2-Diketones by a Transition Metal-Catalyst-Free ReactionSn

TANAKA, M.; KASHIWABARA, T.

BI

RCl

O

O

R1SnBu3

RR1

O

O

R2SnBu3

R2 R1O

Otoluene

3h, 110°C

if R=Cl, slow addition

for R=Cl, R1=Ph

in one portion

R= Ph, Ar, Me, 2-Thienyl, ClR1= allyl, Ph, vinyl, benzyl, Bu, Ph-ethynylR2= allyl, vinyl, Bu, Ph-ethynyl

90-100% 71-78%with 10% of R2=R1

J. Org. Chem. 3958 39612009 74 -, , 10 ,

[Pd]-PEG 400 Catalyzed protocol for the Atom-Efficient Stille Cross-Coupling ReactionSn

ZHOU, W.-J.; WANG, K.-H.; WANG, J.-X.

BI

R'Br4 + SnR4

Pd(PPh3)4 (0.5mol%)

PEG 400, NaOAc, 100°C

R'R4

R=Ph, 48-93%, 25 examplesR=Bu, 42-66%, 5 examples

0.5 to 3 h

Pd

J. Org. Chem. 5599 56022009 74 -, , 15 ,

71


Synthesis of Highly Enantioenriched Chiral αααα-AminoorganotinsSn

COEFFARD, V.; LE GROGNEC, E.; BEAUDET, I.; EVAIN, M.; QUINTARD, J.-P.

BI

O

NBu3Sn

PhSO2Ph

RM (3eq) / BF3.OEt2 (4eq)

Et2O or DCM-78°C

Bu3Sn NOH

R

SO2Ph

Ph

M = Cu, SnR = alkyl, allyl

up to 96% yieldup to >99/1 dr

Cu

J. Org. Chem. 5822 58382009 74 -, , 16 ,

Sex Pheromone of Longtailed Mealybug: A New Class of Monoterpene StructureSn

A [2,3]-sigmatropic rearrangement was used in a key step

MILLAR, J. G.; MOREIRA, J. A.; McELFRESH, J. S.; DAANE, K. M.; FREUND, A. S.

BI

O1) LiAlH4 (89%)

2) KH, ICH2SnBu3

(91%)

O

SnBu3

BuLi

THF, -100°C HO AcO

Li

Org. Lett. 2683 26852009 11 -, , 12 ,

A Straightforward Protocol for One-Pot Allylic Amin ation/Stille CouplingsSn

Stannylated allylic carbonates as building blocks for the diversity-oriented syntheses of functionalized amines.

BUKOVEC, C.; KAZMAIER, U.

BI

SnBu3

OCOOEt[Pd(allyl)Cl]2 (1mol%), PPh3 (8mol%), DMF

1) R1R2NH (1eq), 0°C to rt, 16h

2) R3X (1.2eq), 65°C, 16hR3

N R1

R2

70-96%

Pd

Org. Lett. 3548 35212009 11 -, , 15 ,

Synthesis of 1-Stannacyclopent-3-enes and Their Pyrolysis to StannylenesSn

Kinetics studies revealed the unimolecular dissociation of 1 into 2 and stannylene 3.

ZHOU, D.; REICHE, C.; NAG, M.; SODERQUIST, J.A.; P.P. GASPAR

TT

SnMe2

PhPh

PhPh

CN

CNNC

NCSn

Ph

Ph Ph

Ph

CN

CN

CN

CN

Me2

Ph

Ph

PhCN

CN

CNCN

Ph

+ Me2Sn:

1

- 20°C

32

+

- 10°C


72


Reactivity of a C,N-Chelated StannoxaneSn

In contrast to stannylene 1, its oxidation product 2 is very reactive to CO2 toward give the cyclic compound 3.

PADELKOVA, Z; VANKATOVA, H.; CISAROVA, I.; NECHAEV, M.S.; ZEVACO, T.A.; WALTER, O.; RUZICKA, A.

TT

NMe2

SnO

SnO

(LCN)2 (LCN)2

SnO

O O

Sn

O

(LCN)2(LCN)2

1

= L(LCN)2Sn

O2 CO2

2 3

RT


A Convenient Quick Synthesis of SnBu2RCl DerivativesSn

This method is suitable for the synthesis of compounds 1 that cannot be purified by distillation.

CARRERA, N.; PEREZ-TEMPRANO, M.H.; ALBENIZ A.C.; CASARES, J.A.; ESPINET, P.

TT

1SnBu2R2 + SnBu2Cl2

microwave

irradiation

2 SnBu2RCl

R = C6H4-F-p; C6H4-(OMe)-p; p-tolyl; o- tolyl, mesityl


Molecular StannatelluroxanesSn

The X-ray crystal structure of 1 is reported.

BECKMANN, J.; BOLSINGER, J.; HESSE, M.

TT

O

SnO

Sn

OSn

tBu2

tBu2tBu2

Sn

O

Sn

O

O

R

O

Te

O

R Te

tButBu

tButBu

+ [RTe(O)OH]22/3

R = 2,6-Mes2C6H3 1

Te


Synthesis of 1,1-Bis(trimethylstannyl)cyclopropanesSn

Mechanistic studies reveals that the reaction proceeds via a photoinduced SRN1 mechanism.

GUASTAVINO, J.F.; ROSSI, R.A.

TT

Cl

ClSnMe3

SnMe3

+ 2 Me3SnNa

hν

NH3

+ 2 NaCl


73


A New N->Sn Coordinated Stannonic AcidSn

The discovery of the hydrolytic mechanism of 1 led to the first intramolecularly coordinated stannonic acid 2.

BOUSKA, M.; DOSTAL, L; JIRASKO, R.; RUZICKA, A; JAMBOR, R.

TT

Sn

X

X

X

NMe2

NMe2Me2N

Me2N

R = , H2O6

X = CF3CO2

+ 18 KOtBu

THF

- 18 KO2CCF3, - 18 tBuOH

[RSn(OH)O6]6

1 2


Stille Cross-Coupling Reaction of VinylcyclopropylstannaneSn

PATTENDEN, G.; STOKER, D. A.

LGE

OTf

X

+Bu3Sn

X

Pd(OAc)2, Ph3AsCuI, LiCl,

NMP, 80°C, 24hX

+

X = H, yield = 70%, ratio = 100/0X = OH, vinyl or allyl then yield = 40% and ratio = 50/100

X = H, OH, (E)-CH=CHCO2Et,(E)-CH2CH=C(Me)(CH2)2CO2Et, CH2CH=CH2

Synlett 1800 18022009 -, , 11 ,

Tetrasubstituted Naphtalene Diimides by Stille Cross-Coupling ReactionSn

SURARU, S.-L.; WÜRTHNER, F.

LGE

N

NO O

OO

R1

R1

R1

R1

N

NO O

OO

Br

Br

Br

Br

R1SnBu3

N

NO O

OOR2

R2 R2

R2

Pd(PPh3)4Pd(dba)2, Ph3As

R2 SnBu3

C8H17

C8H17

C8H17

C8H17

C8H17

C8H17

R2 = Ph, SiMe3

Pd(PPh3)4toluene

R1 = Ph, 4-MeOC6H4, 4-NCC6H4

Pd

Synthesis 1841 18452009 -, , 11 ,

Strecker-Type Reaction Using Tributyltin CyanideSn

XIE, Z.; LI, G.; ZHAO, G.; WANG, J.

LGE

R1CHO + R2NH2 + Bu3SnCNNHR2

CNR1

Carboxylique acid

H2O-MeCN (9:1), rt

19 examplesyields = 58 to 100%

Synthesis 2035 20392009 -, , 12 ,

74


Synthesis of (Z)-αααα-Arylsulfonyl- αααα,ββββ-Unsaturated KetonesSn

YOU, S.; LI, J.; CAI, M.

LGE

SO2ArRR

H

SO2Ar

SnBu3

Bu3SnHPd(PPh3)4 (1 mol%)

benzene, rt

R = n-Bu, Ar = Ph, yield = 90%R= n-Bu, Ar = 4-MeC6H4, yield = 88%R = n-Bu, Ar = Ph, yield = 82%

R

H

SO2Ar

OR1

R = n-Bu, PhAr = Ph, 4-Me-C6H4R1 = Ph, 4-O2NC6H4, 4-ClC6H4, 4-MeC6H412 examples, yields = 78-87%

R1COClPd(PPh3)4 (5 mol%)

CuI (75 mol%)

benzene, reflux

PdCu

Tetrahedron 6863 68672009 65 -, , 34 ,

C-nor-D-homosteroids Synthesis via a Radical Cyclisation of Vinylcyclopropane DerivativesSn

PATTENDEN, G.; STOCKER, D. A.; WINNE, J. M.

LGE

PhSe Bu3SnH, AIBN

benzene, 80°C

H

H

HO

Tetrahedron 5767 57752009 65 -, , 29-3

,

Cationic Organobismuth Complex as an Efficient Catalyst in Mannich Reaction Bi

Highly efficient Mannich reaction in water

QIU, R.; YIN, S.; ZHANG, X.; XIA, J.; XU, X.; LUO, S.

MVI

S

Bi

[ClO4]

Chem. Commun. 4759 47612009 -, , 31 ,

Asymmetric Bifonctional Catalysis using Multimetallic SystemsRv

SHIBASAKI, M.; KANAI, M.; MATSUNAGA, S.; KUMAGAI, N .

GN

Review > 35 references

LaLiK

Acc. Chem. Res. 1117 11272009 42 -, , 8 ,

75


Arylation of Carbon-hydrogen BondsRv

DAUGULIS, O.; DO, H.-Q.; SHABASHOV, D.

GN


PdCu

Acc. Chem. Res. 1074 10862009 42 -, , 8 ,

Mechanistic Insights on the Cycloisomerization of Polyunsaturated PrecursorsRv

SORIANO, E.; MARCO-CONTELLES, J.

GN


AuPt

Acc. Chem. Res. 1026 10362009 42 -, , 8 ,

Hydrocarbon Conversion on Metal SurfacesRv

regioselectivity in Alkyl dehydrogenation, stereoselectivity in alkene cis-trans isomerization, enantioselectivity indouble-bond hydrogenationZAERA, F.

GN


NiPt

Acc. Chem. Res. 1152 11602009 42 -, , 8 ,

Transition Metal-Catalysed, Direct and Site-Selective Arylation of the Indole NucleusRv

JOUCLA, L.; DJAKOVITCH, L.

LF

Review

Adv. Synth. Catal. 673 7142009 351 -, , 5 ,

76


Carbonylations of Aryl Halides Catalyzed by PalladiumRv

BRENNFÜHRER, A.; NEUMANN, H.; BELLER, M. ISSUE 23, 4114-4133

CY

A review

Pd

Angew. Chem. Int. Ed. 4114 41332009 48 -, , 23 ,

Palladium(II) Catalysis: C–H Activation and Cross-coupling ReactionsRv

CHEN, X.; ENGLE, K. M.; WANG, D.-H.; YU, J.-Q. ISSUE 28, P5094-5115

CY

A review

Pd

Angew. Chem. Int. Ed. 5094 51152009 48 -, , 28 ,

Pd(II)-Catalyzed Oxidations with Molecular Oxygen as the Sole OxidantRv

GLIGORICH, K. M.; SIGMAN, M. S.;

BJL

This Feature article highlights some of the recent developments in oxygen-coupled PdII-catalyzed oxidation reactions with an emphasis on enhanced catalytic systems and new reactions.

Pd

Chem. Commun. 3854 38672009 -, , 26 ,

Aerobic Functionalization of Pt(II) and Pd(II) Mono alkyl ComplexesRv

VEDERNIKOV, A. N.

BJL

This feature article summarizes the progress achieved in the field of aerobic functionalization ofPt(II) monoalkyl complexes in protic solvents. These functionalization reactions are possible in the presence of tripodal semi-labile ligands. A ‘‘fast’’ acetoxylation of benzylic C–H bonds catalyzed by homogeneous Pd complexes with O2 as the sole oxidant is also presented.

PtPd

Chem. Commun. 4781 47902009 -, , 32 ,

77


CarbenesRv

ARDUENGO, A.J.; BERTRAND, G. (GUEST EDITORS)

EJ

Special issue about carbenes: 15 articles

1 article about heavier analogues of carbenes

Chem. Rev. 3209 38842009 109 -, , 8 ,

Cyclisation of Alkynes with External Nucleophiles Catalysed by Electrophilic MetalsRv

48 references

ABU SOHEL, S. M.; LIU, R.-S.

MVI

FG

RNu

catalyst

catalyst: Au(I), Au(III), Pt(II), Ru(II), W(0)

Functionalised carcocyclic products

Chem. Soc. Rev. 2269 22812009 38 -, , 8 ,

Asymmetric (Transfer) Hydrogenation and Hydrosilylation of Ketones Catalyzed by FeRv

58 references

MORRIS, R. H.

MVI

RR1

O

H2

Me2CHOH

R3SiH H3O+

RR1

H OHFe

Chem. Soc. Rev. 2282 22912009 38 -, , 8 ,

Recent Advances in Aryl–Aryl Bond Formation by Direct ArylationRv

117 references

MCGLACKEN, G. P.; BATEMAN, L. M.

MVI

Ar Ar

X H

ArAr

Ar Ar

H H

Chem. Soc. Rev. 2447 24942009 38 -, , 8 ,

78


A novel Coordination Mode in Porphyrin-Like ChemistryRv

59 references

CUESTA, L.; SESSLER, J. L.

MVI

π-Metal complexes of tetrapyrrolic systems

Chem. Soc. Rev. 2716 27292009 38 -, , 9 ,

Iron(III) Chloride in Oxidative C–C Coupling Reacti onRv

107 references

SARHAN, A. A. O.; BOLM, C.

MVI

RFeCl3

R

R

R

Scholl Reaction

Chem. Soc. Rev. 2730 27442009 38 -, , 8 ,

Combining Transition Metal Catalysis and OrganocatalysisRv

SHAO, Z.; ZHANG, H.

MVI

Transition Metal Catalyst

Organocatalyst

Dual catalysisNew C-C and C-X bond

Chem. Soc. Rev. 2745 27552009 38 -, , 9 ,

Synthetic Applications of Cationic Iron and Cobalt Carbonyl ComplexesRv

A perspective

BROMFIELD, K. M.; GRADÉN, H.; LJUNGDAHL, N.; KANN, N.

MVI

Fe(CO)3

X NuOH

R'R

R''(OC)6Co2

Nu

R'R

R''

Dalton Trans 5051 50612009 -, , 26 ,

79


Palladium-Catalysed Cross-Coupling ReactionsRv

MCGLACKEN, G. P.; FAIRLAMB, I. J. S.

BJL

Palladium cross-coupling reactions and side reactions that have been exploited in synthetic chemistry are discussed.

Pd

Eur. J. Org. Chem. 4011 40292009 -, , 24 ,

Recent Applications of Acyclic (Diene)iron Complexes and (Dienyl)iron CationsRv

DONALDSON, W. A.; CHAUDHURY, S

LF

Microreview

More than 56 references

Fe

Eur. J. Org. Chem. 3831 38432009 -, , 23 ,

On the Behavior of Amines in the Presence of Pd0 and PdII SpeciesRv

MUZART, J.

LF

Review

Pdpt

J. Mol. Catal. A 15 242009 308 -, , 1-2,

C-3 Selective Substitution Reactions of GlycalsZn53

RAWAL, G. K.; RANI, S.; KUMARI, N.; VANKAR, Y. D.

LE

O

CHOBnOOBn

OBnZnCl2 5eq.

Ac2O/AcOH

CH2Cl2

O

CHOBnOOAc

OBn

78%

J. Org. Chem. 5349 53552009 74 -, , 15 ,

80


Use of Chiral Nanoparticles as Catalytic MaterialsRv

ROY, S.; PERICÀS, M. A.

AE

Highlights, 30 references

PdAuRhRuCu

Org. Biomol. Chem. 2669 26772009 7 -, , 13 ,

Reactions of Silylenes with AcetylenesRv

.

ATWELL, W.H.

EJ

Review: 63 references

Si


The Aza-Claisen RearrangementRv

Review covers the last nine years.

MAJUMDAR, K.C.; BHATTACHARYYA, T.; CHATTOPADHYAY, B.; SINHA, B.

GJ

Review with ~ 160 references

AuZnRuPdB

Synthesis 2117 21422009 -, , 13 ,

81

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