ddata.over-blog.comddata.over-blog.com/xxxyyy/3/59/81/73/Archives-2008/...Bibliographic Notebooks For Organometallic Chemistry 2008, 26, ( 4) Li N-Metalated Imines as Intermediates

Bibliographic Notebooks For Organometallic Chemistry 2008, 26, ( 4)

N-Metalated Imines as Intermediates for Pyrimidine and Cyclopentenone CompoundsLi

High yields in most cases

BLANGETTI, M.; DEAGOSTINO, A.; PRANDI, C.; ZAVATTARO, C.; VENTURELLO, P.

MVI

ArCNOEt

OEtLiC-KOR

Ar-CN OEt

MN Ar

PhCOCl

O

Ar NHCOPh

N

NAr Ar

OEt

M = Li, KAmberlyst-15

K

Chem. Commun. 1689 16912008 -, , 14 ,

Dianion Equivalent from Acylsilanes for Substituted ββββ-Keto Esters SynthesisLi

GALLIFORD, C. V.; SCHEIDT, K. A.

MVI

O

SiZ3R N2

Li CO2R1 OLi

Z3SiR

N2

CO2R1

OSiZ3

RCO2R1

Li

CZ3SiO

R OEt

OLi R2X

R3X

O

RCO2R1

R2 R3

Brook

-N2

Chem. Commun. 1926 19282008 -, , 16 ,

Disubstituted Pyridine SynthesesLi

VANDROMME, L.; REISSIG, H.-U.; GRÖPER, S.; RABE, J. P.

CC

NBr NAr RNAr Cl (or Br)

i) ArB(OH)2, K2CO3, Pd(PPh3)4, dioxane/H2O, reflux

ii) [nBuLi/LiDMAE], hexane then CBr4 or C2Cl6

RX, Mg, I2 (cat), Et2O,

Fe(acac)3, THF/NMP

BMgFe

Eur. J. Org. Chem. 2049 20552008 -, , 12 ,

Dynamic Behaviour of Arylallylic Lithium Compounds by X-Ray and NMRLi

FRAENKEL, G.; CHEN, X.; GALLUCCI, J.; REN, Y.

MVI

NO

O Li+

H

Transition state :

J. Am. Chem. Soc. 4140 41452008 130 -, , 12 ,

1


Chiral Lithiated IntermediatesLi

HOGAN, A.-M. L;. O’SHEA, D. F.

CC

NHBn

R

R'NHBn

R

O O

NLi

R

R'

Li

Bn

N

R

(CH2)3OH

R'

Bn

MeOH

R = H, F, OMe R' = Et, nHex, nBu

20 examplesYields = 15-76% er 92:8

i) PhLi (1 eq), cumene, rt, 15 min.

ii) R'Li (2 eq), (-)-spartene (3 eq), -15°C, 4h

for example

i)

ii) HCl (aq)

J. Org. Chem. 2503 25092008 73 -, , 7 ,

Diastereoselective Metalated Nitrile AlkylationLi

FLEMING, F. F.; LIU, W.; GHOST, S.; STEWARD, O. W.

CC

R

CN CN

ERi) LDA (1.05 eq), THF, -78°C, 50 min.

ii) E+ (1.2 eq), THF, -78°C, 3h

R = Me, Ph Yields = 52 - 88%

Mg

J. Org. Chem. 2803 28102008 73 -, , 7 ,

Regio- and Stereoselective Lithiation of 2,3-DiphenylaziridinesLi

Multinuclear NMR investigation is reported.

CAPRIATI, V.; FLORIO, S.; LUISI, R.; MAZZANTI, A.; MUSIO, B.

CC

NPh

Ph

Pr

NPh

Li

Pr

Ph

NLi

LiNPh

Ph

Pr Ph

Ph

LL

L L

NPh

E

Pr

PhNPh

Pr

E

PhL = TMEDA

sBuLiTMEDA

toluene

sBuLi

THF

E+ E+

J. Org. Chem. 3197 32042008 73 -, , 8 ,

Synthesis of Trisubstituted AllenesLi

ZHAO, J.; LIU, Y.; MA, S.

CC

R

HAr

H R

R'Ar

H R' = aryl, alkenyl

R = nC5H11, nC6H13

Ar = Ph, Tol, pMeOC6H4

i) LDA (2 eq), -78°C to rt, 1hii) ZnBr2 (4 eq), rt, 20 min.

iii) Pd(PPh3)4 (5 mol%) R'I (0.8 eq), rt

16 Examples Yields = 56 - 92%

ZnPd

Org. Lett. 1521 15232008 10 -, , 8 ,

2


Trans-1,4-DiphosphacyclohexaneLi

MORISAKI, Y.; IMOTO, H.; OUCHI, Y.; NAGATA, Y.; CHUJO, Y.

CC

PP

Me

MeRR

BH3

BH3

PP

RR

BH3

BH3

PP

RRP

PCH2Li

CH2LiRR

BH3

BH3

sBuLi, THF

(-)-sparteine

(S,S)-isomer trans trans

i) CuCl2

ii) NH3aq

-BH3

Org. Lett. 1489 14922008 10 -, , 7 ,

Asymmetric Deprotonation of N-Boc-PyrrolidineLi

STEAD, D.; O’BRIEN, P.; SANDERSON, A.

CC

N

Boc

N

N

tButBu

N

Boc

i) sBuLi (1.3 eq), Et2O, -78°C, 3h

ii) CuCN.2LiCl (0.5 eq), -78°C, 1hiii) CH2=CHCH2Br (1.8 eq), rt, 16h

(1.3 eq)

Yield = 78% er : 85/15

Org. Lett. 1409 14122008 10 -, , 7 ,

Diborylethyne SynthonLi

KANG, Y. K.; DERIA, P.; CARROLL, P. J.; THERIEN, M. J.

CC

Cl

Cl H

Cl

OB

OiPrO

BO

O

OB

OOR

RO

I

I

OR

RO n

i) nBuLi (3 eq), THF/Et2O, -78°C then 12h, rt

ii) Et2O/THF, 4h, -78°C then 2h, rtiii) anhydrous HCl, -78°C then rt Yield = 77%

(R = -(CH2)3SO3Na)

Pd(OAc)2 (1.5 mol%)/TPXTS1.5 M aq NaOH, µw,150°C, 90 min.

TXPTS = tris(4,6-dimethyl-3-sulfonatophenyl) phosphine trisodium salt

B

Org. Lett. 1341 13442008 10 -, , 7 ,

Stable Hypercarbon CB62- -Based Cluster-Assembled Complexes : CpM(CB6)

q-Li

YANG, L.-M.; HE, H.-P.; DING, Y.-H.; SUN, C.-C.

LS

B C BBB

BB

Computational study : a general strategy for designing stable hypercarbon CB62--based

cluster-assembled compounds CpM(CB6)q- (M = Li, Na, K, Be, Mg and Ca) is proposed. Various sandwich-type interactions are studied.

BNaKBeMgCa

Organometallics 1727 17352008 27 -, , 8 ,

3


Electrophilic Trapping of Dilithio(hetero)arenes.Li

Sequential electrophilic trapping reactions are described leading to desymmetrization of dilithio(hetero)arenes.

MUSCHELKNAUTZ, C.; SAILER, M.; MÜLLER, T. J. J.

BP

Br-(hetero)arylene-Br E1-(hetero)arylene-E21) 2 equiv. n-BuLi (TMEDA), THF, -78 °C, 30 min.

2) Electrophile E1, -78 °C, 3 h3) Electrophile E2, -78 °C, 40 min.

8 examples, yields 39-63 %

Synlett 845 8482008 -, , 6 ,

s-BuLi/(-)-Sparteine-Mediated Chiral Deprotonation of a Piperazine.Li

MCDERMOTT, B. P.; CAMPBELL, A. D.; ERTAN, A.

BP

NNO

ONN

O

Os-BuLi, (-)-sparteineCO2, Et2O, -78 °C

HO2CHATU, DIPEADMF, 25 °C

NNO

O

ON

NBn

48 % over 2 steps, er = 89:11

Synlett 875 8792008 -, , 6 ,

Synthesis of 2,5-Disubstituted 3-(Methylsulfanyl)thiophenes.Li

FATTUONI, C.; USAI, M.; CADONI, E.; CABIDDU, M. G.; DE MONTIS, S.; CABIDDU, S.

BP

S

S CH3 1) BuLi (2.5 equiv.), THF, -78 °C

2) R1X3) R2X

S

S CH3

R1 R212 examples, yield : 25-69 %

Synthesis 985 9892008 -, , 6 ,

Synthesis of Sulfonyl Azides.Li

KATRITZKY, A.; WIDYAN, K.; GYANDA, K.

BP

R-M + SO2

Bt-Cl, Et3NR S

O

O

BtNaN3

MeCNR S

O

O

N3

Bt = Benzotriazol-1-yl

14 examplesYields 23-90 %

M = Li, MgCl, MgBr

Mg

Synthesis 1201 12042008 -, , 8 ,

4


Lithiation of Acenaphthylene and Reaction with Carbonyl Compounds.Li

Lithiation of acenaphthylene catalyzed by 4,4’-di-tert-butylbiphenyl (DTBB).

LILLO, V. J.; GÓMEZ, C.; YUS, M.

BP

1) Li, DTBB (7.5 mol%), -70 °C

2) R1R2CO, -70 to -30 °C3) H2O, - 30 °C to r.t.

OH OHR1

R2R1

R2

OHR1

R2

60-84%1:0-1:12

9 examples

Synthesis 1241 12482008 -, , 8 ,

Polysubstituted PyrrolesLi

DAVIS, F. A.; BOWEN, K. A.; XU, H.; VELVADAPU, V.

CC

N

O

R Y

Boc

N

O

R Y

R'

Boc

N

OH

R Y

H

R'

Y = COOMe, P(O)(OMe)2

i) LDA (3 eq), THF, -78°C, 1h

ii) R'X (1.5 eq),THF, 2h

i) TFA

ii) SiO2, air

8 ExamplesYields = 40 - 88%

R = Ph, tBu, 2-furyl

Tetrahedron 4174 41822008 64 -, , 19 ,

Regioselective Reductive Opening of Non-Symmetrically Substituted PhthalansLi

GARCIA, D.; FOUBELO, F.; YUS, M.

CC

O

R

X

OHR

i) Li (10 eq), DTBB (5 mol%), -78°C or -78°C to -50°C, THF, 3h.

ii) E+, -78°Ciii) H2O, -78°C to rt

Numerous Examples Yields = 25 - 95%

R = H, Ph or OMe

Tetrahedron 4275 42862008 64 -, , 19 ,

1,2-Spiroannelated Five-Membered RingsLi

WIDJAJA, T.; FITJER, L.; MEINDL, K.; HERBST-IRMER, R.

CC

OOH

Li

OOH

i) CeCl3 (2 eq), THF, 2h, 0°C

ii) (1.25 eq), 30 min., rt

77%

Tetrahedron 4304 43122008 64 -, , 19 ,

5


One-Pot Oxidative C-C Bond FormationLi

MATSUO, J.-I.; TANAKI, Y.; ISHIBASHI, H.

CC

NH

R

H

N

R

NH

R

Nui) nBuLi (1.3 eq), THF, -78°C, 15 min.

ii) PhS(Cl)=NtBu (1.5 eq), THF, -78°C, 30 min.

Nu-H (1.6 eq), THF

-78°C, 30 min.

R = Ar, vinyl, CH=CHPh Yields = 36 - 84%

Tetrahedron 5262 52672008 64 -, , 22 ,

Alkyllithium - Lithium Methoxide Mixed AggregatesLi

Computational study is reported.

PRATT, L. M.; KWON, O.; CHI HO, T.; VAN NGUYEN, N.

CC

(R-Li)n + (RO-Li)n (R-Li)x (RO-Li)y

Tetrahedron 5314 53212008 64 -, , 22 ,

αααα-Substituted Monoalkyl- and DialkylbenzenediphosphonatesLi

TVERDOMED, S. N.; RÖSCHENTHALER, G.-V.; KALINOVICH, N.; LORK, E.; DOGADINA, A. V.; IONIN, B. I.

CC

(EtO)2P

(EtO)2P

CH3

R

O

O

(EtO)2P

(EtO)2P H

O

O

F

(EtO)2P

(EtO)2P CH3

O

O

F

OHi) LDA (2 eq), THF, -80°C, 30 min.

ii) for example E+ = pFC6H4CHO

R = H, CH3

for R = Hfor R = CH3

Yield = 45%Yield = 30%

or

Tetrahedron 5306 53132008 64 -, , 22 ,

γγγγ-Organoselenium and γγγγ-OrganotelluriumLi

OKORONKWO, A. E.; ROSARIO, A. R.; ALVES, D.; SAVEGNAGO, L.; NOGUEIRA, C. W.; ZENI, G.

CC

R H R YOH( )n

i) nBuLi (1 eq), THF, -78°C, 1h

ii) Y0 (1 eq) (0°C or 70°C)iii) Br(CH2)nOH (0.5 eq), rt

R = alkyl, aryl Y = Se, Ten = 2, 3, 6

Numerous examples Yields = 19 - 97%

SeTe

Tetrahedron Lett. 3252 32562008 49 -, , 20 ,

6


Synthesis of 1,2-Aminoalcohols by [2,3]-Wittig RearrangementsLi

BARBAZANGES, M.; MEYER, C.; COSSY, J.

CC

R

NTs

OH

SiMe3

PhCH2

PhCH2

N

O

R

SiMe3Ts

LDA, THF, -78°C

R = Me, CH2OPMB

Yields = 76 - 87% dr = 9/1- 10/1


Addition of Ethyl Lithiodiazoacetate to AldehydesLi

LI, P.; MAJIRECK, M. M.; KORBOUH, I.; WEINREB, S. M.

CC

R

OH

N2

CO2Et

Li

N2 CO2Et R

O

N2

CO2Et

RCHOTHF, -78°C

Yields = 42 - 96%

DMP

CH2Cl2, rt


1-Alkynyl CyclopropanolLi

AN,Y.; LIU, J.; JIANG, H.-Y.; WANG, Y.; CHEN, Z.

CC

SO2PhOHR Li

OH

R

Yields = 44 - 90 % (2.0 eq),

THF, 2h, -30°C


Epoxides for Use in Lateral Metalation of Isoxazoles Li

NELSON, J. K.; BURNS, C. T.; SMITH, M. P.; TWAMLEY, B.; NATALE, N. R.

CC

O

R

LiN O

O N

CH3

CH3CH3


7


Transmetallation Behaviour of [M(P4HR4)] Salts toward Rhodium(I) and Copper(I)Na

First targeted synthesis of a transition metal complex containing a tetraphosphanide anion

S. GOMEZ-RUIZ, R. WOLF, E. HEY-HAWKINS

CM

[Na2(THF)4(P4Mes4)]1/ HCl, 1 eq

2/ [{RhCl(COD)}2][Rh(P4HMes4)(cod)] [Rh2(µ-P2HMes2)(µ-PHMes)(cod)2]+

26% 16%

+ other unindentified products

(cod)Rh

P P

PP

MesHMes

MesMes

KRhCu

Dalton Trans 1982 19882008 -, , 15 ,

Efficient Synthesis of 1,3-Oxathiolane-2-thionesNa

This one-pot synthesis is promoted by catalytic sodium hydride and methanol.

YAVARI, I.; GHAZANFARPOUR-DARJANI, M.; HOSSAINI, Z.; SABBAGHAN, M.; HOSSEINI, N.

OS

O

Me HCS2

SO

Me H

S

MeOH+

NaH (10 mol%)96%

Synlett 889 8912008 -, , 6 ,

New Route to 1,2-Diamino-4,5-phthalodinitrile .Na

BURMESTER, C.; FAUST, R.

BP

NS

NNC

NC

NaBH4, EtOH

r.t., 24 h, 53 %

NC

NC

NH2

NH2

Br

Br

NH2

NH2

Synthesis 1179 11812008 -, , 8 ,

Synthesis of a Mixed Alkali Metal BorohydrideK

Tuning the decomposition temperature in complex hydrides; applications in hydrogen storage

E. A. NICKELS, M. OWEN JONES, W. I. F. DAVID, S. R. JOHNSON, R. L. LOWTON, M. SOMMARIVA, P. P. EDWARDS

CM

LiK(BH4)2 X-ray characterizationThermogravimetric studies

Li

Angew. Chem. Int. Ed. 2817 28192008 47 -, , 15 ,

8


Selective ββββ-HydroxyethylationMg

Various substituted epoxides were coupled with modest to excellent yields, under these conditions.

SIEGMUND, A.; RETZ, D.; XI, N.; DOMINGUEZ, C.; BÜRLI, R.; LIU, L.

OS

NN

O

OH

O

BnOO

NH

N

OO

BnO

92%

CHCl3, 35 °C, 16 h.

Mg(ClO4)2 1 equiv.+

10 equiv.

Synlett 1005 10082008 -, , 7 ,

Triorganozincates Addition to N-(tert-butanesulfinyl)imines.Mg

Triorganozincates as nucleophiles for diastereoselective addition to N-(tert-butanesulfinyl)imines.

ALMANSA, R.; GUIJARRO, D.; YUS, M.

BP

Ph H

NS

But

O

Ph R(R')

HNS

But

O

1) RMgBr-R'2Zn (1.5 equiv.)

2) NH4Cl (aq.)

dr up to 98:2, 14 examples, yields 28-99 %R, R' = Me, Et, n-C5H11, iPr, vinyl

Zn

Tetrahedron Asymm. 603 6062008 19 -, , 5 ,

Constrained Geometry Rare-Earth Metal Complexes: Synthesis and Catalytic Application.Sc

Mechanistic studies are presented. Catalytic activity increases with metal ionic radius.

ZHANG, W. X.; NISHIURA, M.; MASHIKO, T.; HOU, Z.

GR

LnSiN

Ar

NMe2

(THF)n

Ar= 2,4,6-Me3C6H2Ln= Y, La, Pr, Nd, Sm, Gd, Lu : n=1)Ln= Sc: n= 0

catalytic application: PH

R2

R1 N

C

N

R3

R4

+ P C

R2

R1 N

HN R4

R3

13 examples

YLaPrNdSmGd

Chem. Eur. J. 2167 21792008 14 -, , 7 ,

Bis(Oxazolinyl)Pyridine Scandium Complexes for Asymmetric Diels–Alder Reactions.Sc

Electron-withdrawing Pybox substituents give rise to higher enantioselectivity.

WANG, H.; WANG, H.; LIU, P.; YANG, H.; XIAO, J.; LI, C.

GR

O

NRO

O+

cat.R

O N O

O

R=H, Me

NO

N N

O

Sc(OTf)3

X

R' R'

cat:R'= iPr, Ph, tBu, Bn

X= H, Cl, Br, OMe, NMe2

ee up to 96%

J. Mol. Catal. A 128 1312008 285 -, , 1 ,

9


Anilido-Phosphinimine Dimethyl Scandium Complexes.Sc

Various C-H bond activation processes are observed, upon thermal treatment or under hydrogen atmosphere.

CONROY, K.D.; PIERS, W. E.; PARVEZ, M.

GR

PR2

N NAr

Li

ScCl3(THF)3 PR2

N NAr

Sc

MeLi

Cl Cl

PR2

N NAr

Sc

Me Me

J. Organomet. Chem. 834 8462008 693 -, , 5 ,

Isoprene Polymerization with Yttrium Amidinate Catalysts.Y

Change in selectivity upon AlMe3 addition is explained by the formation of heterobimetallic Y/Al species.

ZHANG, L.; NISHIURA, M.; YUKI, M.; LUO, Y.; HOU, Z.

GR

N

Y

N

Ph

ArAr

R R

Ar: 2,6-iPr2C6H3

R: CH2(o-C6H4NMe2)

cat:[CPh3][B(C6F5)3]

cat. / AlMe3 (>3eq)

n

1,4-cis-PI > 98%

[CPh3][B(C6F5)3]

cat.

n

iso-3,4-PI > 99%

Al

Angew. Chem. Int. Ed. 2642 26452008 47 -, , 14 ,

New Chiral Lanthanide Amide Ate Complexes for Intramolecular Hydroamination.Y

The countercation nature is shown to exert an influence on the system peformances (Li>K).

AILLAUD, I.; COLLIN, J.; DUHAYON, C.; GUILLOT, R.; LYUBOV, D.; SCHULZ, E.; TRIFONOV, A.

GR

N

NLn

R

R

N

N

R

R

[M(THF)n]

Ln= Yb: R= c-C6H11, c-C5H9, CH2tBu, iPrLn= Y: R= c-C5H9, iPrM= Li, K

NH2

nRR cat.

RR

NHn cat:

9 substratesee up to 87%

YbLiK

Chem. Eur. J. 2189 22002008 14 -, , 7 ,

Zeolite NaY-Promoted Cyclisation of FarnesalY

TSANGARAKIS, C.; LYKAKIS, I. N.; STRATAKIS, M.

LS

Me

MeMe

O

Me

HMe

Me

Me

CHOMe Me

O

MeMe

NaY

70°C, 3h+

1a (d.r. = 92/8)1b(E)/1c(Z)

1a/1b/1c = 5/4/182% yield

J. Org. Chem. 2905 29082008 73 -, , 7 ,

10


Synthesis of 4-Alkoxy-2-aryl-1,2,3,4-tetrahydro-quinoline DerivativesCe

10 examples, yields: 67-77%; imino Diels-Alder (Povarov) reaction.

SRIDHARAN, V.; AVENDANO, C.; MENENDEZ, J.C.

GJ

NH2

CHO OEt

NH

H

H

OEt(NH

4)2Ce(NO

3)6

+ +

72%

(5 mol%)

MeCN, rt, 45 min

Synthesis 1039 10442008 -, , 7 ,

Construction of Cyclopenta[b]benzofuran Skeleton Involving Reductive CouplingSm

A route to racemic rocaglamide and its 2,3-di-epi analogue is described.

LI, H.; FU, B.; WANG, M. A.; LI, N.; LIU, W. J. ; XIE, Z. Q. ; MA, Y. Q.; QIN, Z.

OC

O

O

OMe

OMe

MeO O

OMe

MeO

OH CONMe2

HO

OMe

O

OMe

MeO

OH CONMe2

HO

OMe

+

1. PhCH=C(COOMe)22. SmI2, us

3. Me2NLi, −78 °C4. Me4NBH(OAc)3

Eur. J. Org. Chem. 1753 17582008 -, , 10 ,

Reaction of Ketenes with Lanthanocene Amide and Imidazolate Complexes.Yb

Crystal structures of the complexes have been determined.

LIU, R.; ZHENG, P.; WENG, L.; ZHOU, X.; LIU, C.

GR

C OPh

Ph

[Cp2Ln(C3H3N2)]2 NN LnCp2

O

Ph

Ph

N NCp2Ln

O

Ph

Ph

[Cp2Ln(NHnBu)]2Cp2Ln

ON

nBuPh

Ph

LnCp2

ON

nBuPh

PhH

H

ErDy

J. Organomet. Chem. 1614 16202008 693 -, , 8-9,

Bridgeg Half-sandwich Titanium ComplexesTi

XIAO T.; WANG J.; ZHANG Y.; GAO W.; MU Y.

GN

Synthesis, structures and catalytic properties for ethylene polymerization of bridgeg titanium complexes.

OTMS

R2

R1

TMS

Ph H

O

R2R1

PhH

TiCl

Cl

TiCl4

J. Organomet. Chem. 1195 12022008 693 -, , 7 ,

11


Titanium Tetraisocyanide ComplexesTi

ALLEN J.M.; ELLIS J.E.

GN

Reaction of the Ti(0) carbonyl anion [CpTi(CO) 4]- with I 2, Ph3SnCl, and Me 3SnCl in the presence of four equivalents of CNXyl, where Xyl = 2,6-dimethylpheny l, affords titanium tetraisocyanides complexes, [CpTi(CNXyl) 4E], E = I, SnPh 3, SnMe3, which have been characterized by IR and NMR spect roscopy and single-crystal X-ray crystallography.

Sn

J. Organomet. Chem. 1536 15422008 693 -, , 8-9,

Synthesis of Homoallyl Ethers and ChloridesTi

MERISOR, E.; CONRAD, J.; MALAKAR, C. C.; BEIFUSS, U.

BJL

ROH + HC(OMe)3

Lewis acid

RX X: Cl or OMe

InBiB

Synlett 903 9072008 -, , 6 ,

Enantioselective Hetero-Diels-AlderTi

LI, X.; MENG, X.; SU, H.; WU, X.; XU, D.

BJL

OMe

Me3SiO

+ RCHO

1. Ti-L* additive

2. CF3CO2H

O

O R

43-99%, 11-84% ee

L*:OHN

OH

Synlett 857 8602008 -, , 6 ,

Chemioselective Oxidation of Secondary AlcoholsTi

SHEI, C.T.; CHIEN, H. L.; SUNG, K.

BJL

R1 R2

OH

R1 R2

OTiCl4/TBHP (0.1:1.7)

60-85%

Synlett 1021 10262008 -, , 7 ,

12


Ti(IV) Reductive AminationTi

SALMI, C.; LONCLE, C.; LETOURNEUX, Y.; BRUNEL, J. M.

CC

R R'

O

OHNH2

R R'

NHOH

+i) Ti(OiPr)4 (1.3 eq), MeOH, rt, 5-6h

ii) NaBH4 (1 eq), 0°C, 2h then rt, 20 min.(3 eq)

10 ExamplesYields = 11 - 89%

Tetrahedron 4453 44592008 64 -, , 19 ,

Synthesis of Optical Activity Analysis of Chiral Titanium(IV)Ti

Asymmetric methylation of benzaldehyde was studied with chiral group IV sec-butoxides.

MACMILLAN, S. N.; LUDFORD, K. T.; TANSKI, J. M.

TJ

MN

N

N

N

M = Ti, Zr, Hf

OH

*M

O

O

O

O

*

*

*

*

+C6H6

example:Ti(OR-2Bu)4:

[α]D = -83.1 10-1degcm2g-1

ZrHf


Regio- and Stereoselective Preparation of Dienylcarboxylic AcidsTi

OGATA, A.; NEMOTO, M.; TAKANO, Y.; TSUBOUCHI, A.; TAKEDA, T.

TJ

R1

SO2Me

FG

R2

+R1 FG

R21. Cp2Ti[P(OEt)3]2

2. H2O

FG = CO2Li, PO(OEt)2

R1 = Ph, C6H13, CH2CH2PhR2 = CH3, C6H13, CH2CH2Ph

14 examples59-86%

2E > 91%


Interconversion of Zirconaaziridine EnantiomersZr

Kinetic measurements

CUMMINGS, S. A.; TUNGE, J. A.; NORTON, J. R.

BPH

NCp2Zr

R2

R1N

Cp2Zr

R2

R1

OO

O

Ph Ph OCp2Zr

NR1

R2

OO Ph

Ph

k1

k2

J. Am. Chem. Soc. 4669 46792008 130 -, , 14 ,

13


Catalytic Asymmetric Alkylations of KetoiminesZr

R1 = Ar, Alk, R2 = CO2Me, CF3

FU, P.; SNAPPER, M. L.; HOVEYDA, A. H.

BPH

R1 R2

N

MeO

Chiral ligand (0.1 equiv)Zr(Oi-Pr)4, i-PrOH (0.1 equiv)

Me2Zn (4 equiv)toluene, 22 °C, 48 h

R1 R2

HN

MeO

Me

79-97% ee

chiral ligand :

t-Bu

OHt-Bu

NH

i-Pr

O BnNHBu

O

J. Am. Chem. Soc. 5530 55412008 130 -, , 16 ,

Formal SN2’ SubstitutionZr

Scope and mechanism detailed

LALIC, G.; KRINSKY, J. L.; BERGMAN, R. G.

BPH

OR+

N-TBS

OCp2Zr

R1R2

1) C6D6, 23 °C

2) Cbz-Cl

NHCBz

R2

R1

76-99%

In similar conditions : E isomers : <20% yield

J. Am. Chem. Soc. 4459 44652008 130 -, , 13 ,

Linear Triene FormationZr

Also three examples of tetraenes !

KANNO, K.; IGARASHI, E.; ZHOU, L.; NAKAJIMA, K.; TAKAHASHI, T.

BPH

R1 R1

+R2 R2 Cp2ZrCl2

2 EtMgBrCp2Zr

R1

R1

R2R2

1) NCS

2) R3 R3

CuCl, 0 °C3) H+

R3R1

Cl

R3R1

R2 R2

R1 = Alk, R2 = Ar, R3 = CO2R32-64% (isolated)

Cu

J. Am. Chem. Soc. 5624 56252008 130 -, , 17 ,

(Amidomethyl)pyridine Zirconium and Hafnium Complex esZr

NIENKEMPER K.; KEHR G.; KEHR S.; FROHLICH R.; ERKER G.

GN

NR2

HN

R1

Ar

R3

NR2

N

R1

Ar

R3

(NMe2)3Hf

Hf(NMe2)4Zr(NMe2)4NR2

N

R1

Ar

R3

(NMe2)3Zr

Substituted N-arylaminoalkylpyridine derivatives we re synthesized and used as ligands for (chelate ligand) MX3 systems (M = Zr,Hf). Some of these gave very active ethene polymerization catalysts.

Hf

J. Organomet. Chem. 1572 15892008 693 -, , 8-9,

14


Synthesis and Reduction Behavior of Novel Sandwich Complexes of ZirconiumZr

BELOV S.A.; KIRSANOV R.S.; KRUT’KO D.P.; LEMENOVSKII D.A.; CHURAKOV A.V.; HOWARD J.A.K.

GN

ZrCl

Cl

N(CH3)2

Me3Si

Me3Si ZrH

Me3Si

Me3SiNCH3

Mg/Hg, THF

20°C, 5 days

J. Organomet. Chem. 1912 19182008 693 -, , 10 ,

Detailed Mechanisms on Insertion of cis-2-butene into Zr-H Bond of Cp2ZrH 2Zr

BI S.; KONG X.; ZHAO Y.; ZHAO X.; XIE Q.

GN

Cp2*Zr

H

H

Cp2*Zr

H

+

The mechanisms for both the side-insertion and the central-insertion of cis-2-butene into the Zr-H bond of Cp2ZrH2 to give Cp2Zr(H)(CH2CH2CH2CH3) were explored with the aid of DFT calculations.

J. Organomet. Chem. 2052 20602008 693 -, , 11 ,

Use of ZrO(OTf)2 as Catalyst for Trimethylsilylation of Alcohols with HMDSZr

MOGHADAM M.; TANGESTANINEJAD S.; MIRKHANI V.; MOHAMMADPOOR-BALTORK I.; CHAHARDAHCHERIC S.;TAVAKOLI Z.

GN

2 R-OH + Me3SiNHSiMe3

ZrO(OTf)2

ACN2 R-OSiMe3 + NH3

Rapid and efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane catalyzed by reusable zirconyl triflate [ZrO(OTf)2] is reported. Primary, secondary and tertiary alcohols as well as phenols were efficiently converted to their corresponding TMS ethers.

J. Organomet. Chem. 2041 20462008 693 -, , 11 ,

Reactions of MCl4(PMe3)2 Complexes (M = Hf, Nb) with Cyclohexadienyl AnionHf

HARVEY B.G.; BASTA R.; ARIF A.M.; ERNST R.D.

GN

Nb PMe3Hf PMe3

Nb

J. Organomet. Chem. 1420 14252008 693 -, , 8-9,

15


Oxidative Coupling of 2-NaphtholsV

TAKIZAWA, S.; KATAYAMA, T.; KAMEYAMA, C.; ONITSUKA, K.; SUZUKI, T.; YANAGIDA, T.; KAWAI, T.; SASAI, H.

GJ

OH

OH

OHO

N

V OO

O

N

VOO

O O OHOH

CH2Cl2, 0°C,

72 h

catalyst (5 mol%), air

catalyst

Chem. Commun. 1810 18122008 -, , 15 ,

Cyclopentadienyl-Silyl-Amido and Imido Niobium Complexes. Nb

Reaction outcome depends on the amine nature; DFT calculations have been performed to support experimental results.

MAESTRE, M. C.; MOSQUERA, M. E. G.; JACOBSEN, H.; JIMÉNEZ, G.;CUENCA, T.

GR

MCl ClCl

Cl

SiMe2ClR-NH2

MClClCl

SiMe2Cl

MCl NCl

SiMe2Cl

N

R

R


Agostic Distortions in Early-Transition-Metal Alkyl Complexes.Nb

DFT studies are presented.

PANTAZIS, D. A.; MCGRADY, J. E.; BESORA, M.; MASERAS, F.; ETIENNE, M.

GR

[Nb]

HC

H3C

CH2

Me

Ph

H [Nb]

CH3C

CH3

Me

Ph

H

vs. [Nb]= [HB(Me2pyr)3]NbCl

β-agostic interaction α-agostic interaction


Unexpected Formation of (Dimethylaminomethylene)Methylamide Complexes.Nb

No definitive mechanism for the formation of the amido-amine ligand could be proposed.

ZHANG, X.-H.; CHEN, S.-J.; CAI, H.; IM, H.-J.; CHEN, T.; YU, X.; CHEN, X.; LIN, Z.; WU, Y.-D.; XUE, Z.-L.

GR

MCl5 + 5 LiNMe2 M(NMe2)5 + MMe2N

Me2N NMe2

NMe2

NMe2

MeNM= Nb, Ta

Ta


16


Zwitterionic Niobium and Tantalum Imido Complexes.Nb

Theoretical and methyl methacrylate polymerization studies are presented.

ARTEAGA-MÜLLER, R.; SÁNCHEZ-NIEVES, J.; RAMOS, J.; ROYO, P.; MOSQUERA, M. E. G.

GR

MCl3(NR)(Py)2

MCl2(NR)(OAr)(Py)2

LiOAr

BnMgCl

BnMgClN

M

R

Ph

PhPh

N

MO

R

Ph

ArPh

THF

E(C6F5)3

E(C6F5)3

2 eq.

M = Nb, TaR = tBu, 2,6-iPr2C6H3Ar = 2,6-iPr2C6H3E= B, Al

N

M

R

Ph

Ph E(C6F5)3

N

MO

R

Ph

Ar E(C6F5)3-(THF)E(C6F5)3

TaZr


Non-Oxidative Coupling Reaction of Methane to Ethane and Hydrogen.Ta

Catalysis by a silica-supported tantalum hydride.

SOULIVONG, D.; NORSIC, S.; TAOUFIK, M.; COPÉRET, C.; THIVOLLE-CAZAT, J.; CHAKKA, S.; BASSET, J.-M.

BP

2 CH4> 250 °Ccat.,

C2H6 + H2 cat. :

Si

O

Si

OTa

H

J. Am. Chem. Soc. 5044 50452008 130 -, , 15 ,

Linear Ta-H-B Geometry. Ta

Crystal structure of the complex shows an essentially linear Ta–H–B interaction.

HILL, A. F.; SMITH, M. K.; WAGLER, J.

GR

TaCl Cl

Cl

Cl+ 2 B

H HSS

Na

BH H

SS BNNN N

S SH H

Na

=TaCl

B

H

H SHHSNa

V IV


[8+2] and [8+3] Cyclisations of Alkenyl CarbenesCr

BARLUENGA, J.; GRACIA-RODRIGUEZ, J.; MARTINEZ, S.; SUAREZ-SOBRINO, A. L.; TOMAS, MIGUEL

PG

NOMe[M]

R'

R

+

NR

H

R'

CO2Me

[M] = Cr(CO)5or W(CO)5

7 examples79-91%

NR

O

HR'[8+2] [8+3]

9 examples21-85%

W

Chem. Asian J. 767 7752008 3 -, , 4 ,

17


Carbene Complexes: Enantiopure Aminocarbenes of CrCr

MECA, L.; CISAROVA, I.; GRAHONOVSKY, D.; DVORAK, D.

RE

MeO2C

CH3 Cr(CO)5

NMé2

(S)-1-(1-naphthyl) ethanol

O2C

CH3 Cr(CO)5

NMé2

MeO2C

CH3 Cr(CO)5

NMé2

1) crystalisation2) MeOH


Selective cis-Dihydroxylation of OlefinsMo

Recyclable homogeneous molybdenum acetylide catalyst

A. V. BIRADAR, B. R. SATHE B, S. B. UMBARKAR, M. K. DONGARE

CM

R R' R R'

OHHOCpMo(CO)3(C CPh)H2O2

tBuOH, 65°Cconv: 45-92%

J. Mol. Catal. A 111 1192008 285 -, , 1-2,

Tungsten Allyl Complexes and AminesW

[W] = WCp*, Cp* = C5Me5

TSANG, J.Y.K.; BUSCHHAUS, M.S.A.; FUJITA-TAKAYAMA, C.; PATRICK, B.O.; LEGDZINS, P.

RF

[W] CH2tBu

ON

NH

N

[W] CH2tBu

NO

- H2


Directed Formation of Allene Complexes .Mn

Formation of a 1:1 mixture of syn/anti isomers, each characterized by X-ray analysis.

SENTETS, S.; SERRES, R.; ORTIN, Y.; LUGAN, N.; LAVIGNE, G.

HJR

Mn

OC

Tol

PhCO

Mn

OC CO

1) LiPCy2, / THF, -80°C2) CF3SO3H / THF, -80°C-r.t.

H

PCy2Ph

Tol

Brown crystals, 55%

Mn

OC CO Ph

Tol H

PCy2

+

Yellow crystals, 26%

O


18


Supported Pyrazole Rhenium ComplexesRe

Catalysts for cyclohexane oxidation with O2

G. S. MISHRA, E. C. B. ALEGRIA, L. M. D. R. S. MARTINS, J. J. R. FRAUSTO DA SILVA, A. J. L. POMBEIRO

CM

O OH

+

[ReClxFy{N2C(O)Ph}(pyrazole)z(PPh3)k]

immobilized on 3-aminopropyl functionalized silica

O2

no solvent, no additive

overall conversion = 16% max

J. Mol. Catal. A 92 1002008 285 -, , 1-2,

Reduction of 2,2'-Bipyrimidine in the Self-Assembly of Metal-Based Rectangles.Re

Partially reduced ligand unambiguously characterized by 1H NMR and X-ray analysis.

WU, J.-Y.; THANASEKARAN, P.; CHENG, Y.-W.; LEE, C.-C.; MANIMARAN, B.; RAJENDRAN, T.; LIAO, R.-T.; LEE, G.-H.;PENG, S.-M.; LU, K.-L.

HJR

N

N

N

N+ Re2(CO)10+ pyrazine

Re

CO

CO

OC

NN

NN

Re

CO

OC

OC

Re

CO

CO

NN

NN

Re

COOC

N-L-N

N-L-N CO

CO

N-L-N = pyrazine

Purple crystals, 67%

C4H9OH, 160 °C, 48 h


Ferrocenyl Complexes: in vitro Biological Effect Against Breast CancerFe

HEILMANN, J.B.; HILLARD, E.A.; PLAMONT, M.-A.; PIGEON, P.; BOLTE, M.; JAOUEN, G.; VESSIERES, A.

RE

Fe

RR

J. Organomet. Chem. 1716 17222008 693 -, , 8,9,

Ferric-Chloride-catalyzed Reductive Halogenation of Carbonyl Compounds.Fe

Synthesis of bromides and iodides from keto compounds.

LI, Z.; SHENG, C.; YANG, C.; QIU, H.

CB

R

O

R'MeCl2SiH

(1.5 equiv)

+5% FeCl3

PBr3 (1.1 equiv)

NaI (1.5 equiv)

R

Br

R'

R

I

R'

CH3CN

reflux / 4-10h

reflux / 6-24h

42-97%

71-95%

Org. Prep. Proc. Int. 608 6112007 39 -, , 6 ,

19


Synthesis of αααα-Oxo ThiocyanatesFe

15 examples, yields: 68-84%.

YADAV, J.S.; REDDY, B.V.S.; REDDY, U.V.S.; CHARY, D.N.

GJ

O OFeCl

3SCN

CH2Cl2, rt, 40 min

78%

Synthesis 1283 12872008 -, , 8 ,

Characterization of Intermediates Relevant to Ring Closing Metathesis Catalysis.Ru

Spectroscopic characterization of ruthenacyclobutane and ruthenium olefin carbene intermediates are given.

VAN DER EIDE, E. F.; ROMERO, P. E.; PIERS, W. E.

BP

N NMesMes

RuCl

ClCH

PR3 A

N NMesMes

RuClCl

C

CC

H

HH CO2Me

CO2Me

α

βαH

J. Am. Chem. Soc. 4485 44912008 130 -, , 13 ,

Ru-Cat Dienyne Synthesis from 1,3-Dienes and Propargylic Alcohols Ru

DAINI, M.; YOSHIKAWA, M.; INADA, Y.; UEMURA, S.

PG

Ar

OH

R

R

Ar

R

R

+ Ru Ru

S

SCl

*Cp

iPr

iPr

Cp*

Cl

Ru-Cat (5 mol %)NH4BF4 (10 mol %)

ClCH2CH2Cl60°C, 1 h

7 examples67-80%

Ru-Cat :


New Highly Active Bimetallic Precatalyst for Alkene Metathesis Ru

VINOKUROV, N.; GARABATOS-PERERA J. R.; ZHAO-KARGER, Z.; WIEBCKE, M.; BUTENSCHÖN, H.

PG

NMesMesN

Ru

OiPr Cr(CO)3

ClCl


20


Triosmium and Triruthenium Carbonyl ClustersOs

Activation of two C-H bonds of NHC N-methyl groups.

J. A. CABEZA, I. DEL R¾O, D. MIGUEL, E. PEREZ-CARRENOC, M. G. SANCHEZ-VEGA

CM

Os Os

Os

N

N

CH3

CH3= CO

Toluene, 110°C

5hOs Os

Os

NNCH3C

H

H H

Ru

Dalton Trans 1937 19422008 -, , 14 ,

Hydride Complexes of Osmium and RutheniumOs

Preparation of chelate vinyl derivatives by reaction with propargylic alcohols

G. ALBERTIN, S. ANTONIUTTI, A. BACCHI, G. PELIZZI, G. ZANARDO

CM

P

Os

PCP

P OP

Os

PCP

PC

HH

H

R

Ph

+

C

O C

H

H

H

R

Ph+

+HC CCPh(R)OH

OsH(κ1-OTf)P4

Ru

Eur. J. Inorg. Chem. 1913 19202008 -, , 11 ,

Triosmium and -Ruthenium ClustersOs

LI C.; LEONG W.K.

GN

Os Os

OsOH

HOs Os

OsE

H

Os Os

OsE

H

OsOs

OsE'

H

The reaction of triosmium and -ruthenium clusters with bifunctional ligands carrying -OH, -SH and -COOH groups is described. The structure of eight of the compounds obtained have also been determined.

+ E'HHE

E'H

+

Ru

J. Organomet. Chem. 1292 13002008 693 -, , 7 ,

Osmium Carbyne ComplexesOs

LEE J-H.; PINK M.; SMURNYY Y.D.; CAULTON K.G.

GN

The mechanism of conversion of terminal alkynes RCCH to coordinated carbyne OsCCH2R by Os(H)2ClXL2 (L =

PiPr3) has been studied for X = OTf and B(ArF)4 (ArF = 3,5-di(CF3)2(C6H3). The energy of various intermediates,

including the only experimentally unobserved one, η2-vinyl, was evaluated with DFT(PBE) calculations.

Os

L

L

CH2R

XCl

HOs(H)2ClL2X + RCCH

X = OTf or BAr4

B

J. Organomet. Chem. 1426 14382008 693 -, , 8-9,

21


New Triosmium-iridium ClustersOs

Synthesis and molecular structure of new osmium-iridium mixed-metal clusters

LEE Y-B.; WONG W-T.

GN

OsOH

Os

Os

Ir

COCO

COOC

CO

Ir

OC

OC

OC

CO

ClOC OsOH

Os

Os

Ir

COCO

COOC

ClOC

OC

OC

CO

COOC

Ir

J. Organomet. Chem. 1528 15352008 693 -, , 8-9,

Pauson-Khand Reactions with Tricobalt Carbonyl ClustersCo

good yields but low enantiomeric excess

MOBERG, V.; MOTTALIB, M. A.; SAUER, D.; POPLAVSKAYA, Y.; CRAIG, D. C.; COLBRAN, S. B.; DEEMING, A. J.;NORDLANDER, E.

MVI

EtOOCEtOOC

CO OEtOOCEtOOC P P

[Co3(µ3-CH)(CO)7(R,R-DuPhos) *

R,R-DuPhos

Dalton Trans 2442 24532008 -, , 18 ,

Cyclotrimerisation of Phenylacetylene with Co Catalysts Containing Disulfide LigandsCo

HILT, G.; HENGST, C.; HESS, W.

OC

Ph

3

Ph

Ph Ph Ph

Ph

PhCo(ligand)Br2

Zn, ZnI225 °C, < 30 min

S S PhPh

NN cHexcHex

ligand: 2.9 : 1

1 : 19.2

96 % in CH2Cl2

99 % in CH3CN

+

Eur. J. Org. Chem. 2293 22972008 -, , 13 ,

Co-Catalyzed Hydrolytic Kinetic Resolution (HKR) of EpoxidesCo

RAJ, I. V. P.; SUDALAI, A.

CC

O

R

O

RYields = 46-47% ee = 94-98%

(R,R)- or (S,S)-Co(III)salen.OAc (0.5 mol%),

H2O (0.55 eq), rt

R = Ph or pMeOC6H4


22


Styrene Hydroformylation.Rh

Influence of the position and lenght of the R group on the selectivity.

GUO, Y.; FU, H.; CHEN, H.; LI, X

MJ

CHO

CHO

Rh(acac)(CO)2 (cat.)

CO/H2 (1:1, 1.5 Mpa)

PhMe, 50 °C

MeO P

R

R

(2eq./Rh)

+

Catal. Commun. 1842 18452008 9 -, , 9 ,

Asymmetric Hydroformylation of meso-Bicyclic HydrazinesRh

BOURNAUD, C.; LECOURT, T.; MICOUIN L.; MÉLIET, C.; AGBOSSOU-NIEDERCORN, F.

OC

NCOR

NCOR

NCOR

NCORHO

1. Rh(acac)(CO)2 (1 mol%) L* (2 mol %) H2/CO (1:1) Toluene

2. NaBH4 MeOH

up to 77.5 % ee

N

PPh2

Ph2P

Boc

L*:

(S,S)-BPPM

Eur. J. Org. Chem. 2298 23022008 -, , 13 ,

Catalytic Rhodium Nitrene/Alkyne MetathesisRh

THOMTON, A. R.; BLAKEY, S. B.

PJF

OSO2NH2

BnO

O

NHS

O

OBn

O O

Rh2(esp)2, PhI(OAc)2

Then NaBH4, MeOH

71%

J. Am. Chem. Soc. 5020 50212008 130 -, , 15 ,

Mechanism of Rhodium Catalyzed Aldehydes DecarbonylationRh

Kinetic studies and DFT calculations

FRISTRUP, P.; KREIS, M.; PALMELUND, A.; NORRBY, P.-O.; MADSEN, R.

PJF

O RhCl (5 mol%), dppp

diglyme, Reflux

J. Am. Chem. Soc. 5206 52152008 130 -, , 15 ,

23


New Abnormal N-Heterocyclic Carbene Rhodium and Iridium ComplexesRh

M = Ir, Rh

SONG, G.; ZHANG, Y.; LI, X.

PJF

MCl

N

N

R


Base Free C=X ReductionIr

CORBERAN, R.; PERIS, E.

PJF

O

N

N

Ir

nBu

nBu

X

X ClCl

OH

iPrOH


Asymmetric Ni-Catalyzed Conjugate Allylation of Activated EnonesNi

The mechanism is discussed

SIEBER, J. D.; MORKEN, J. P.

MVI

O

Ar pentyl

B(pin)O

Ar pentylP

O

O

O

O

Ar Ar

Ar Ar

Ph5 mol% Ni(cod)2

1.5 equiv

toluene, rt91-94% ee10 mol% L

Ar = 3,5-di-t-butylphenyl

J. Am. Chem. Soc. 4978 49832008 130 -, , 14 ,

Ni-Catalyzed Addition of C-H Bonds of Terminal Alkynes to 1,3-Dienes and StyrenesNi

The regiochemistry is discussed

SHIRAKURA, M.; SUGINOME, M.

MVI

PhSiiPr3 Ph

SiiPr3

Ni(cod)2 (1-10 mol%)PBu3 (P/N = 4)

toluene, rt96%

J. Am. Chem. Soc. 5410 54112008 130 -, , 16 ,

24


Ni/NHC-Catalyzed CycloadditionsNi

Cycloadditions of diynes and carbonyl reagents are reported ; mechanisms are proposed.

TEKAVEC, T. N.; LOUIE, J.

CC

O

R

R'

( )n

R

( )n O

R

R"R'

( )n

n = 1,2

Ni(cod)2 (10 mol%),

IPr (15 mol%),toluene, rt, R'COR"

Ni(cod)2 (5 mol%),

SIPr (10 mol%),toluene, rt, R'CHO

Yields = 67-97% Yields = 77-98%

J. Org. Chem. 2641 26482008 73 -, , 7 ,

Ni-Catalyzed AllylationNi

SUMIDA, Y.; HAYASHI, S.; HIRANO, K.; YORIMITSU, H.; OSHIMA, K.

CC

OBocR

R"

ROH

R'R'

R"

R"

R+

Ni(cod)2 (5 mol%),P(OEt)3 (10 mol%),

toluene, reflux, 5h

(1.2 eq)

+

Org. Lett. 1629 16322008 10 -, , 8 ,

Synthesis of Methyl 7-Oxo-1-oxa-6-azaspiro[4.4]nonane-8-carboxylatesNi

10 examples.

SUKHORUKOV, A.YU.; LESIV, A.V.; KHOMUTOVA, Y.A.; IOFFE, S.L.; NELYUBINA, Y.V.

GJ

ON

CH3

CH3

CO2Me

CO2Me

CH3

NO

O

H

CH3

CH3

CH3

CO2Me

NO

O

H

CH3

CH3

CH3

CO2Me

NO

O

H

CH3

CH3

CH3

CO2Me

NO

O

H

CH3

CH3

CH3

CO2Me

+ + +

Raney NiMeOH

H2 (70 bar)

80°C, 2 h

77% (5.4:1.1:4.1:1.0)

Synthesis 1205 12202008 -, , 8 ,

Ni-Catalyzed Carbonylative Negishi Coupling ReactionsNi

WANG, Q.; CHEN, C.

CC

N N

OMeMeO

R

R

R

R

O

1

2

3

4RX

R

R

1

2

3

X = OTf or I

+ R42Zn

CO (1 atm), NiCl2-L (2-5 mol%)

MgBr2 (1.8 eq), DMSO 23-80°C, 20-40 min.

L =

(1.3 eq) Yields = 72 - 95%

Zn


25


Pd-Catalyzed Asymmetric TMM [3+2] Cycloaddition: a HighlightPd

Phosphoramidite ligands (L*) are excellent chirality transfer agents in these reactions.

LE MARQUAND, P.; TAM, W.

CY

OAcTMS RR

*+

Pd cat., L*

[3+2]

(TMM = trimethylenemethane)

Angew. Chem. Int. Ed. 2926 29282008 47 -, , 16 ,

Iterative C–H Bonds Functionalization for the Total Synthesis of AlkaloidsPd

BECK, E. M.; HATLEY, R.; GAUNT, M. J.

CY

NBoc

TMS

HN

N

Et

O

OC–H Pd-cat. alkenylation

C–H Ir-cat. borylation,then Suzuki

rhazinicine

Ir

Angew. Chem. Int. Ed. 3004 30072008 47 -, , 16 ,

Ambitious sp2–sp3 Suzuki Cross-CouplingPd

PATERSON, I.; ANDERSON, E. A.; DALBY, S. M.; LIM, J. H.; GENOVINO, J.; MALTAS, P.; MOESSNER, C.

CY

OO

OMeO

TESOCl

TBSO

I

PMBOOH

OMe

a) 9-BBN, THF; H2O;

b)

PdCl2(dppf), Ph3As,Cs2CO3, THF/DMF (1:1)

OO

OMeO

TESOCl

TBSO

PMBOOH

OMe

Angew. Chem. Int. Ed. 3016 30202008 47 -, , 16 ,

Aryl Ketones Decarboxylative Cross-CouplingPd

GOOΒEN, L. J.; RUDOLPHI, F.; OPPEL, C.; RODRIGUEZ, N.

CY

O

O

OK

OMe

Br+

CuBr (15 mol%), Pd(F6-acac)2 (1 mol%),1,10-phenanthroline (15 mol%),P(o-Tol)3 (2 mol%), NMP/quinoline (3:1)

O

OMe83%

Cu

Angew. Chem. Int. Ed. 3043 30452008 47 -, , 16 ,

26


Hydroarylation of Alkenes with Boronic EstersPd

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

CY

B

F

O

O

[Pd(SiPr)Cl2]2 (0.75 mol%),(–)-sparteine (6 mol%),

tBuOK (6 mol%), iPrOH,O2, 55 ºC, 24 h

+

F

78%

SiPr =NN

iPr

iPr Pri

Pri

Angew. Chem. Int. Ed. 3219 32222008 47 -, , 17 ,

Pd-Catalyzed Hydrogen Transfer Semireduction of AlkynesPd

Good to excellent chemo- and stereoselectivities are obained.

HAUWERT, P.; MAESTRI, G.; SPRENGERS, J. W.; CATELLANI, M.; ELSEVIER, C. J.

CY

R1 R2

R1 R2

Cat. (1 mol%),HCO2H/NEt3 (5 equiv),THF or MeCN, reflux Cat. =

N

NPd

O

O

O

solvent

Angew. Chem. Int. Ed. 3223 32262008 47 -, , 17 ,

Dissolution and Redistribution of Pd over a Pd Foil Used as CatalystPd

Re-deposition of Pd take place at the cool edges of the locally heated reaction zone of the Pd foil in the above modelcross-coupling reaction.MACQUARRIE, S.; HORTON, J. H.; BARNES, J.; MCELENEY, K.; LOOCK, H.-P.; CRUDDEN, C. M.

CY

BO

OO2N I+

Pd foiliPr2NEt, DMF

localized heatingO2N

Angew. Chem. Int. Ed. 3279 32822008 47 -, , 17 ,

Hiyama Cross-Ccoupling Reaction.Pd

Lower yield with NaOH instead of TBAF. No reaction with CsF or KF.

PAN, C.; LIU, M.; ZHAO, L.; WU, H.; DING, J.; CHENG, J.

MJ

Ar1X + Ar2Si(OMe)3PdCl2 (0.05 eq.)

TBAF.3 H2O (1 eq.)PhMe, 100 °C, 10 h

(2 eq.)Ar1-Ar2 X = Br: 80-96%

X = Cl:31-77%

Si

Catal. Commun. 1685 16872008 9 -, , 8 ,

27


Pd-Catalyzed Intramolecular Diamination of AlkenesPd

MUNIZ, K.; HOVELMANN, C. H.; CAMPOS-GOMEZ, E.; BARLUENGA, J.; GONZALES, J. M.; STREUFF, J.; NIEGER, M.

PG

NH

NHTosO

N N Tos

O

RR R

R

Pd(OAc)2 (10 mol %)CuBr2 (3 equiv)K2CO3 (1equiv)

DMF, 40°C

R'

R'

5 examples75-99%

Cu

Chem. Asian J. 776 7882008 3 -, , 4 ,

Reduction of CeriaPd

ACERBI, N.; TSANG, S. C; GOLUNSKI, S. COLLIER, P.

BJL

CeO2 (ceria) is widely used as a catalysts support. The combination of platinum group metals (PGM) with ceria is known to lower the ceria reduction temperature. The authors have been able to demonstrate a direct correlationbetween PGM promotion of the ceria surface and the work function of the metal. An electronic interaction plays acrucial role in the metal-ceria interface.

PtRhRuAg

Chem. Commun. 1578 15802008 -, , 13 ,

Three-Component Coupling of Arynes, Allylic Compound and Terminal AlkynesPd

BHUVANESWARI, S.; JEGANMOHAN, M.; YANG, M.-C.; CHENG, C.-H.

BJL

OTfR1

R2 SiMe3

+ X

R3

R4

R5+ R6

Pd(PPh3)4, CuI

CsF

R1

R2

R3

R4R5

R669-92%

Chem. Commun. 2158 21602008 -, , 18 ,

Pd-domino Sequence for Tricyclic HeterocyclesPd

HU, Y.; SONG, F.; WU, F.; CHENG, D.; WANG, S.

MF

N

O

Br N

O

R

R

Pd(OAc)2 2% / PPh3 4%

nBu3, DMF , 155 °C

R = EWG, EDG

22 Examples

Chem. Eur. J. 3110 31172008 14 -, , 10 ,

28


Pd Nanoparticles Supported on Siliceous Mesocellular Foam for Heterogeneous CatalysisPd

ERATHODIYIL, N.; OOI, S.; SEAYAD, A. M.; HAN, Y.; LEE, S. S.; YING, J. Y.

MF

MCF

OH

OH

OH

HO MCF

OH

OH

HO

HNO

NHR Pd(MeO)3Si

HN

O

NHRPd(OAc)2

Toluene, 60 °C

MCF : Siliceous MesoCellular FoamSuzuki at 80 °CHeck at 100 °C

Hydrogenation at r.t.Reductive Amination at r.t.

ReusableCatalyst

Chem. Eur. J. 3118 31252008 14 -, , 10 ,

Enantioselective Addition of Arylboronic Acids to Cyclic Enones Mediated by NHC-PdPd

ZHANG, T.; SHI, M.

MF

N

N

N

N

PdO

O

O

O

CR3

CR3

Me

Me

R = H, F

O O

ArArB(OH)2

NHC-Pd

KOH, H2O/THF, r.t.

3 %mol

NHC-Pd

Chem. Eur. J. 3759 37642008 14 -, , 12 ,

Pd-catalyzed Three-Components Coupling for Synthesis of DiarylketonesPd

NEUMANN, H.; BRENNFÜHRER, A.; BELLER, M.

MF

Br (HO)2BR1 R2 R1

O

R2COPd(OAc)2 / L P nBu

2.5-10 bars TMEDA, Toluene80-120 °C

L :

Chem. Eur. J. 3645 36522008 14 -, , 12 ,

Phosphite–Oxazoline/Oxazine Ligand for Allylic SubstitutionPd

DIÉGUEZ, M.; PÀMIES, O.

MF

ON O

P

OO

R

R

R

R

RR R

X

R R

Nu

Nu H

Pd/L Cat.

Ligand

Chem. Eur. J. 3653 36692008 14 -, , 12 ,

29


4-(1',3'-Dien-2'-yl)-2,5-dihydrofuran Synthesis from AllenolsPd

DENG, Y.; LI, J.; MA, S.

MF

. R

HOR1

.OH

O

R

R1

PdI2

BF3. Et2ODMSO, 80 °C

Chem. Eur. J. 4263 42662008 14 -, , 14 ,

Homeopathic Catalysts Loading for Suzuki Coupling in WaterPd

FLECKENSTEIN, C. A.; PLENIO, H.

MF

+HP Cy

Cy

SO3H

SO3H

HSO4-

Hydrosoluble Ligand

Na2PdCl4 / LClHeteroAryl

Ar B(OH)2

ArHeteroAryl

0.01-0.05 mol %

100 °C, K 2CO3H2O

Chem. Eur. J. 4267 42792008 14 -, , 14 ,

Contrasting Bonding Modes of a Tridentate Bis(oxazoline)phosphine Ligand Pd

Unprecedented eight-membered ring chelates.

KERMAGORET, A.; BRAUNSTEIN, P.

BS

N

OP

N

O

PhCoFe

Dalton Trans 585 5872008 -, , 5 ,

Pd(II) Complexes with Mixed Benzothiazolin-2-ylidene and Phosphine LigandsPd

Moderate to good catalytic activity in Suzuki-Miyaura coupling reaction of aryl bromides and chlorides.

YEN, S. K.; KOH, L. L.; HUYNH, H. V.; HOR, T. S. A.

BS

Novel Pd(II) mixed N,S-heterocyclic carbene (NSHC)-phosphine complexes

Dalton Trans 699 7062008 -, , 5 ,

30


Pd-catalysed Asymmetric Mono- and Bis-alkoxycarbonylation of VinylarenesPd

GODARD, C.; MUÑOZ, B. K.; RUIZ, A.; CLAVER, C.

BS

Ph+ CO + MeOH

O

OMe

*

Ph

Ph O

OMe

O OMe

*Ph OMe

O

[Pd]/LOxidant

[Pd]/L'L'bidentate

[Pd]/L'L monodentate

Dalton Trans 853 8602008 -, , 7 ,

Pd-cat. Aminations of Aryl Halides with Phosphine-functionalized Imidazolium LigandsPd

SHI, J.-C.; YANG, P.; TONG, Q.; JIA, L.

BS

RX + NR1R2

RNR1R2

Pd(OAc)2/L (0.001 - 0.02 eq.)

L = PPh2

N

NR3Fe

I

Dalton Trans 938 9452008 -, , 7 ,

Cross-Coupling Reactions of Triorganoindium Reagents with Alkenyl HalidesPd

RIVEIROS, R.; SAYA, L.; SESTELO, J. P.; SARANDESES, L. A.

BJL

R1 Br

Br

1. R23In

Pd (cat)

2. R33In

Pd (cat)

R1 R2

R3

50-99%

Eur. J. Org. Chem. 1959 19662008 -, , 11 ,

Synthesis of 2,6-Disubstituted PyridinesPd

The sequence involves Suzuki coupling, ortholithiation/halogenation and Negishi coupling

VANDROMME, L.; REIßIG,H.-U.; SUSIE GRÖPER, S.; RABE, J. P.

BJL

NBr

1. ArB(OH)2, K2CO3

Pd(PPh3)4 (cat)

2. n-BuLi-LiDMAE, C2Cl6

3. Fe(acac)3 (cat), RMgBr NAr R

Fe

Eur. J. Org. Chem. 2049 20552008 -, , 12 ,

31


Aqueous C–C CouplingPd

The immobilized palladium catalyst is leach proof and recyclable

TSVELIKHOVSKY, D.; BLUM, J.

BJL

X

R + Reagents C-C coupling[Pd] cat.

K2CO3

Microemulsion

[Pd]: Pd(OAc)2 entrapped within a hydrophobicitized silica sol–gel matrix

Reagents:R

, ArB(OH)2, PhSnBu3

Ph Ph / PhB(OH)2

BSn

Eur. J. Org. Chem. 2417 24222008 -, , 14 ,

Direct Arylation of EnaminonesPd

GE, H.; NIPHAKIS, M. J.; GEORG, G. I.

CJM

N

O

+ ArBF3K

Pd(OAc)2 30%Cu(OAc)2 3 EqK2CO3 2 Eq.

tBuOH AcOH DMSO60 °C

N

OAr 19 examples

up to 97% yield

J. Am. Chem. Soc. 3708 37092008 130 -, , 12 ,

Porphyrin ComplexesPd

MATANO, Y.; MATSUMOTO, K.; NAKAO, Y.; UNO, H.; SAKAKI, S.; IMAHORI, H.

CJM

N

NN

N

Ar

Ar P

Ar

M

Zn

N

NN

N

Ar

Ar

Zn

PhPh

PPhPh

Ar

M= Pd, Pt

PtZn

J. Am. Chem. Soc. 4588 45892008 130 -, , 14 ,

Catalyst Poisoning in the Cyanation of Aryl HalidesPd

ERHARDT, S.; GRUSHIN, V. V.; KILPATRICK, A. H.; MACGREGOR, S. A.; MARSHALL, W. J.; ROE, D. C.

CJMJ. Am. Chem. Soc. 4828 48292008 130 -, , 14 ,

32


C-C Triple Bond CleavagePd

WANG, A.; JIANG, H.

CJM

R2R1 + R3OH R1COOR3 + R2COOR3

Pd(OAc)2 2%ZnCl2•2H2O 20%

O2 7.5 Atm.R3OH (solvent) 100 °C

J. Am. Chem. Soc. 5030 50312008 130 -, , 15 ,

Arylallenes via a Retropropargylation of Homopropargyl AlcoholsPd

HAYASHI, S.; HIRANO, K.; YORIMITSU, H.; OSHIMA, K.

CJM

ROH+ ArBr

Pd2dba3 2.5%PnOct3 20%Dimethylacetamide 70%KOH 2 equiv.

Toluene, reflux H

• R

Ar

H

J. Am. Chem. Soc. 5048 50492008 130 -, , 15 ,

Enantioselective Intramolecular Heck-Iminium CyclizationPd

Total synthesis of Minfiensine

DOUNAY, A. B.; HUMPHREYS, P. G.; OVERMAN, L. E.; WROBLESKI, A. D.

CJM

NOTf CO2Me

BocHN Pd(OAc)2 L*pentamethylpiperidine

toluene, 100 °C75-85% yield, 89% ee

NCO2Me

BocHN

TFA

NCO2Me

NBoc

J. Am. Chem. Soc. 5368 53772008 130 -, , 15 ,

5-exo-dig Hydroarylation of AlkynesPd

CHERNYAK, N.; GEVORGYAN, V.

CJM

R1

R2 Pd(OAc)2 5%NHC 7%

Toluene, 120°C

R1

R2

18 examples47-98% yield

J. Am. Chem. Soc. 5636 56372008 130 -, , 17 ,

33


Hydroperoxide Formation: MechanismPd

KONNICK, M. M.; STAHL, S. S.

CJM

NHC

PdBzO H

NHC

- BzOH

Slow(NHC)2Pd0

O2, BzOH

Fast

NHC

PdBzO OOH

NHC

J. Am. Chem. Soc. 5753 57622008 130 -, , 17 ,

Autocatalytic Oxidative AdditionPd

Oxidative addition is faster with Pd(II) than with Pd(0)

BARRIOS-LANDEROS, F.; CARROW, B. P.; HARTWIG, J. F.

CJM

Ph-Br(PtBu3)2Pd0

slow

(PtBu3)2PdII(H)Br

fast(PtBu3)Pd(Br)Ph(PtBu3)Pd(Br)Ph

J. Am. Chem. Soc. 5842 58432008 130 -, , 18 ,

Palladium-Catalyzed Hydrostannation of Substituted Propargyl Alcohols.Pd

FARAONI, M. B.; GERBINO, D. C.; PODESTA, J. C.

AM

R

R1HOR2

R

Nph3Sn

R1HO

R2

syn α

RR1

HOR2

syn β

+

SnNph3

Nph3SnH+PdCl2(PPh3)2

THF

Nph = Neophyl = CH2CM2PhR, R1, R2 = H, alkyl, Rh

Sn

J. Organomet. Chem. 1877 18852008 693 -, , 10 ,

Hydrogenation.Pd

Influence of the amount of Pd/C on the selectivity.

LI, X.; MENG, X.; SU, H.; WU, X.; XU, D.

MJ

NH2

OH

(S)

5% Pd/C

H2 (80 bar)EtOH, 80 °C, 10 h

NH2

OH

NH2

OH+

18-33% 48-66%

Synlett 857 8602008 -, , 6 ,

34


Cross-Couplings.Pd

Synthesis of the Se/Te starting materials described.

ALVES, D.; PRIGOL, M.; NOGUEIRA, C. W.; ZENI, G.

MJ

Se Ph

TeBu

Ph Pd(PPh3)4 (0.15 eq.)Ag2O, NEt3

MeOH, reflux, 24 h

71%Pd(acac)2 (0.1 eq.)CuI (0.2 eq.), NEt3MeOH, reflux, 4 h

BF3KPhMeO BF3K

Se PhPh

Se PhPh

PhOMe

68%

AgCuBTeSe

Synlett 914 9182008 -, , 6 ,

Addition to N-Tosylarylimines.Pd

28 examples. Ligand, catalyst, solvent and base screening.

ZHANG, Q.; CHEN, J.; LIU, M.; WU, H.; CHENG, J.; QIN, C.; SU, W.; DING, J.

MJ

N

Ts

Ph

+ PhB(OH)2(2 eq.)

PdCl2(PhCN)2 (0.05 eq.)i-Pr2NPPh2 (0.05 eq.)

K2CO3 (3 eq.), MS 4Ådioxane, 80 °C, 24 h 83%

NH

Ts

Ph

Ph

B

Synlett 935 9392008 -, , 6 ,

Heck Reaction.Pd

Use of these compounds to carry out [3+3] cyclizations.

MROΒ G.; REINKE, H.; LANGER, P.

MJ

Cl

O

EtO

R1

R3

R2

Pd(OAc)2 (0.01 eq.)NEt3 (1.2 eq.)

(4 eq.)

+80 °C, 24 h

6 examples, 32-54%

O

R1

R3

R2

EtO

Synlett 963 9662008 -, , 7 ,

Intramolecular Heck Reaction, 9-endo-trig Cyclization.Pd

6 examples.

MAJUMDAR, K. C.; CHATTOPADHYAY, B.

MJ

MeN

NMe

O

BrO

O

MeN

NMeO

OO

90%

Pd(OAc)2 (0.1 eq.)n-Bu4NBr (1.2 eq.)KOAc (2.75 eq.)

DMF, 100 °C, 2-3.5 h

Synlett 979 9822008 -, , 7 ,

35


Intramolecular Oxidative Coupling.Pd

Various conditions tested. Also from furan derivatives.

BECCALLI, E. M.; BORSINI, E.; BROGGINI, G.; RIGAMONTI, M.; SOTTOCORNOLA, S.

MJ

S N

CO2Et

PdCl2(MeCN)2 (0.15 eq.)CuCl2 (0.15 eq.)

O2, DMF, 100 °C, 2 h

70%

S N

CO2Et

Cu

Synlett 1053 10572008 -, , 7 ,

Tandem [2+1]Cycloaddition-Ring Expansion.Pd

7 examples.

BIGEAULT, J.; DE RIGGI, I.; GIMBERT, Y.; GIORDANO, L.; BUONO, G.

MJ

OAc+

(2 eq.)

Pd(OAc)2 (0.05 eq.)CyPhP(O)H (0.1 eq.)

PhMe, 60 °C60%

OAc

Synlett 1071 10752008 -, , 7 ,

Pd-Cat Synthesis of 3-Indoles Carboxylic Acid DerivativesPd

SÖRDERBERG, B. C. G.; BANINI, S. R.; TURNER, M. R.; MINTER, A. R.; ARRINGTON, A. K.

PG

NO2

CO2R'

RNH

CO2R'

R

Pd(dba)2 (10 mol %)dppp (15 mol %)

1,10--phenatroline (30 mol %)

CO (6 atm), 120°C

10 examples 74-95%

Synthesis 903 9122008 -, , 6 ,

Chiral Phosphoramidites Ligand for Pd-Cat Asymmetric Hydrosilylation of StyrenesPd

LI, X.; SONG, J.; XU, D.; KONG, L.

PG

OO

P

Cl

OMe

SiCl3

R R

HSiCl3 (2 equiv)[Pd(C3H5)Cl]2 (0,125 mol %)

Ligand* (0,5 mol %)

rt, neat

9 examples65-96% yield - 73-97% ee

Ligand* :

Synthesis 925 9312008 -, , 6 ,

36

Bibliographic Notebooks For Organometallic Chemistry2008, 26, ( 4)

Pd-Cat Synthesis of Conjugated Dienes Pd

LEMHADRI, M.; BATTACE, A.; BERTHIOL, F.; ZAIR, T.; DOUCET, H.; SANTELLI, M.

PG

Ph2P PPh2Ph2PPPh2

Br

R''R'

R R'''[Pd(C3H5)Cl]2 (0,5 equiv)

Tedicyp (1 equiv)+

R''R'

R

R'''

Major isomer22 examples

TON up to 66 000

Tedicyp :

Synthesis 1142 11522008 -, , 7 ,

Application of Suzuki Cross-Coupling: Synthesis of Substituted Imidazoles.Pd

PRIMAS, N.; MAHATSEKAKE, C.; BOUILLO, A.; LANCELOT, J-C.; OLIVEIRA SANTOS, J. S.; LOHIER, J-F.; RAULT, S.

AM

N

NH

N

NB

O

O

NH

NAr

1) Suzuki cross-coupling reaction

2) Deprotection

4 steps

THP

B

Tetrahedron 4596 46012008 64 -, , 20 ,

Application of Palladium-Catalyzed Carbonylation.Pd

Formal synthesis of (+)-bakkenolide A using the title reaction is reported.

KATO, K.; MOTODATE, S.; TAKAISHI, S; KUSAKABE, T.; AKITA, H.

AM

R1

OH

O

+-

L* (7.5 mol %)Pd(TFA)2 (5 mol %)

p.benzoquinoneR2OH, CO balloon

O

R1R2O

OCO2R2DMP

oxidation21-23%92-97% ee

45-49%37-46% ee

+R1 = Me, Propyl, allyl

O

R1

OCO2R2

ON N

O

PhL*:

Ph

Tetrahedron 4627 46362008 64 -, , 20 ,

Pd-N-heterocyclic Carbene: Application in Carbon-Carbon Coupling Reaction.Pd

POLSHITTIWAR, V.; VARMA, R.S.

AM

X

R

R Y

R

YHeck reaction

organic Pd-NHC silica

DMF, MW

NNPd

N NII

Si

Si

OOO

OOO

OOO

OOO

R = H, Me, OMe, CHO, COMe, Fe, Cl, thiopheneX = Br, IY = CO2CH3, C6H5

[Pd] :

Tetrahedron 4637 46432008 64 -, , 20 ,

37


Palladium-Catalyzed Alkynes Oxidation.Pd

DMSO-PdI2 as powerful oxidizing couple of alkynes into benzils is reported.

MOUSSET, C., PROVOT, O.; HAMZE, A.; BIGNON, J.; BRION, J-P.; ALAMI, M.

AM

N

N Ar

Ar1Ar Ar1R

PdI2 (2 mol%)

DMSO, 140 °CAr

Ar1O

O

PdI2 (2 mol%)

DMSO, 140 °CNH2

NH2R

Tetrahedron 4287 42942008 64 -, , 19 ,

Palladium-Catalyzed Synthesis of Haloethynyl and Dihalovinyl Analogues of AZT and FLT.Pd

Synthesis and anti-HIV activity of AZT and FLT analogues are described.

JOUBER, N.; AMBLARD, F.; RAPP, K. L.; SCHINAZI, R. F.; AGROFOGLIO, L. A.

AM

O

OH

HO N

NH

O

OO

F/N3

HO N

NH

O

OO

F/N3

HO N

NH

O

O

II

Pd(0) I

X

and/or X = Cl, Br, I

Tetrahedron 4444 44522008 64 -, , 19 ,

Application of Suzuki Cross-Coupling Reaction in Synthesis of Ent-narciclasine.Pd

MATVENKO, M.; BANWELL, M. G.; WILLIS, A. C.

AM

O

O

B

OMOMCO2Me

OO OMOM

NH2

OMOM

OMOMBr+

NHO

O

OR

OOR

OR

OR

Pd(0), base

µ waveTMS-Br

R = MOMR = H

Tetrahedron 4817 48262008 64 -, , 21 ,

A Study of Heck Cyclization Reaction to Form Phenanthridine Ring Systems.Pd

DONALDSON, L. R.; HAIGH, D.; HULME, A. N.

AM

N PN P N P

HH

HH

Br

Hermann-Beller cat.Ag2CO3, DMF, ∆, <2h

P = SO2Me, BocCbz, Bn

Hermann-Beller cat.MeNCy2, MeCN, ∆, <5h

or Pd2(dba)3/tBu3PHBF4

MeNCy2, MeCN, <50°C

Ag

Tetrahedron 4468 44772008 64 -, , 19 ,

38


Selective C3-Arylation of Free NH-IndolesPd

CUSATI, G.; DJAKOVITCH, L.

TJ

NR1

H NR1

H

R2

R1 = H, Ph, CH3

+ Br R2K2CO3 3 equiv.

1 mol% [Pd(NH3)4]2+/NaYdioxane, reflux

24-48 h 18-95% conversions15-85% isolated yields

R2 = H, Cl, OCH3

CH3, NO2


Synthesis of 1,2-DihydroisoquinolinesPd

NAKAMURA, H.; SAITO, H.; NANJO, M.

TJ

NR2

R1

N

R1

R2

CCl3

2.5 mol % [Pd]5 mol% dppe

CHCl3, 100 °C

R1 = n-Bu, Ph, Cy2NCH2

R2 = Ar, Bn, n-Pr

12 examples32-99%


Regioselective Heck ArylationPd

LIU, Z.; XU, D.; TANG, W.; XU, L.; MO, J.; XIAO, J.

TJ

X

R RNHAc

3 mol% Pd(OAc)26 mol% DPPP

Et3N 2 equiv.[H2NiPr2][BF4] 4 equiv.

isopropanol, reflux

13 examples32-93%

+ NHAc


Direct C-H Activation/Functionalisation Reaction of HeteroaromaticsPd

GOTTUMUKKALA, A. L.; DERRIDJ, F.; DJEBBAR, S.; DOUCET, H.

TJ

O

N

or SO

N

or SR1

R3R2

5 mol % PdCl(C3H5)(dppb)

DMF, Cs2CO380-140 °C

BrR1

R3R2

+ 11 examples27-69%


39


Synthesis of 2,3-Dihydro-1H-pyrrolo[3,2-c]quinolinesPd

TOMASZEWSKI, M. J.; WHALLEY, A.; HU, Y.-J.

TJ

X

NH2

R4

R3

R2

R1

R4

R3

R2

R1N

N

OO

CHO

N

OO

+Pd(PPh3)4, K2CO3

Dioxane, microwave1 h, 170 °C

13 examples14-74%

X = I, Br


Synthesis of 4,6-Substituted CoumarinsPd

FERNANDES, T. A.; CARVALHO, R. C. C.; GONÇALVES, T. M. D.; DA SILVA, A. J. M.; COSTA, P. R. R.

TJ

R1

OHI

+ RCO2Et

O O

R1

R

H2O, Et3N, PdCl2

E or ZR1 = Cl, NO2,CO2Et

OOR = Me,

or Pd(OAc)270 °C, 40 h 6 examples, 44-90%


Pd-Catalyzed Indolization of 2-BromoanilinesPd

CUI, X.; LI, J.; FU, Y.; LIU, L.; GUO, Q.-X.

TJ

R1Br

NHR

+N

Rs

RL R

Rs

RL

Pd(OAc)2 1 mol%Phenylurea 4 mol%

K2CO3, DMF130 °C, 30 h

R1

14 examples55-86%

R = H, Me, AcR1 = H, Me

Rs, RL = Alkyl, Ar


A PCP-Pincer Liganded Anionic Platinum(0) ComplexPt

SCHWARTSBURD, L.; COHEN, R.; KONSTANTINOVSKI, L.; MILSTEIN, D.

CY

Pt

PtBu2

PtBu2

ClNa, THF

Pt

PtBu2

PtBu2

– Na+

Angew. Chem. Int. Ed. 3603 36062008 47 -, , 19 ,

40


Chemoselective Hydrogenation of ChloronitrobenzenePt

WANG, F.; LIUAB, J.; XU, X.

BJL

NO2

Cl

+ H2

[Pt] cat.[Pt]: Pt supported on Ag/γ-Zr(PO4)(NH4HPO4)

H2

NH2

Clselectivity 100%, up to 26000 TON

Chem. Commun. 2040 20422008 -, , 17 ,

Platinated-Copper Complexes as DNA Cleaving and Cytotoxics AgentsPt

OZALP-YAMAN, S.; DE HOOG, P.; AMADEI, G.; PITIÉ, M.; GAMEZ, P.; DEWELLE, J.; MIJATOVIC, T.; MEUNIER, B.;KISS, R.; REEDIJK, J.

MF

N NO

O

NNN

NNO

O

NN N

Pt

Cl

Cl

CuCl2 CuCl2H H

HH

Cu

Chem. Eur. J. 3418 34262008 14 -, , 11 ,

Tandem Intramolecular Hydroalkoxylation–Hydroarylat ion ReactionsPt

BARLUENGA, J.; FERNÁNDEZ, A.; SATRÚSTEGUI, A.; DIÉGUEZ, A.; RODRÍGUEZ, F.; FAÑANÁS, F. J.

MF

OH O O

R1 R1 R1

R2 R2 R2

Hydroalkoxylation Hydroarylation

AuI or PtII or PtIV

Au

Chem. Eur. J. 4153 41562008 14 -, , 14 ,

Reactivity of Pt- and Pd-bound Nitriles Towards Nitrile Oxides and NitronesPt

KUZNETSOV, M. L.; KUKUSHKIN, V. Y.; POMBEIRO, A. J. L.

BS

O

NN

R'

R

M

2

O

NCH3N

R'

R

M

2

R'C N-O

N CR)2M

R'C N-O M2

M O-NCHR'

CH3 2

M = Pd, Pt; [M] = trans-[MCl2]

Pd

Dalton Trans 1312 13222008 -, , 10 ,

41


Pt(II) Schiff Base as Versatile Phosphorescent Core ComponentPt

TONG, W.-L.; LAI, L.-M.; CHAN, M. C. W.

BS

OHC

OC7H14

C7H14O

OC7H14

C7H14O

O

N NH

CHO

C7H14O

OC7H14

C7H14O

OC7H14

O

OC7H14H14O7

Pt

Dalton Trans 1412 14142008 -, , 11 ,

Rational Design of Platinum(II) and Gold(III) Compl exes as Antitumour AgentsPt

WANG, X.; GUO, Z.

BS

Au

Dalton Trans 1521 15322008 -, , 12 ,

Azobenzene DiborationPt

BRAUNSCHWEIG, H.; KUPFER, T.

CJM

FeB

B

NMe2

NMe2

+N

N

Ph

Ph

Pt(PEt3)3 5%

Toluene 120 °C

FeB

B

NMe2

NMe2

NN

Ph

Ph

FeB

J. Am. Chem. Soc. 4242 42432008 130 -, , 13 ,

Cycloisomerization.Pt

5 examples.

KATO, K.; KOBAYASHI, T.; FUJINAMI, T.; MOTODATE, S.; KUSAKABE, T.; MOCHIDA, T.; AKITA, H.

MJ

Ph(CH2)2

AcO

1) Cat. (0.05 eq.)PhMe, rt, 48 h

2) Na2CO3 MeOH

O

(CH2)2Ph

Cat = AuCl3 (43%), PtCl4 (49%)

Au

Synlett 1081 10852008 -, , 7 ,

42


Cu-Cat Three-Component Coupling Reaction: 2-Functionnalization of PyrroleCu

CHO, S. H. CHANG, S.

PG

17 examples, 54-91% yield

R

R' SO2N3

NH

R''

HN

R''R

NSO2R'

RN•

LnCu

SO2R'

NR''CuCl (10 mol %)

Et3N (1.2 equiv)

CHCl325°C, 2 h

Angew. Chem. Int. Ed. 2836 28392008 47 -, , 15 ,

Asymmetric Cu-Cat Propargylic AminationCu

DETZ, R. J.; DELVILLE, M. M. E.; HIEMSTRA, H.; VAN MAARSEVEEN, J H.

PG

R

OAc

+ ArNH2R

HNArCuI (10 mol %)

Ligand* (12 mol %)DIPEA (4 equiv)

MeOH, -20°C

14 examples62-97% yield / 13-87% ee

N

OO

N

Ph Ph

Ligand*

Angew. Chem. Int. Ed. 3777 37802008 47 -, , 20 ,

Cu-Catalyzed Domino Four-Component Coupling and Cyclization ReactionCu

OHTA, Y.; OISHI, S.; FUJII, N.; OHNO, H.

MD

+

CHO

(HCHO)nR2NH

then t-BoNH2

CuI (10 mol%)

DMF N

NR2

10 examples60-88% yield

Chem. Commun. 835 8372008 -, , 7 ,

Bio-Inspired Dicopper Catalyst Complex for Selective Benzylic C-C CouplingCu

PROKOFIEVA, A.; PRIKHOD’KO, A.; DECHERT, S.; MEYER, F.

MD

OHdicoppercomplex

OH

OH

1/2

dicoppercomplex

O

O

1/2O2

Chem. Commun. 1005 10072008 -, , 8 ,

43


Reaction of Diazoalkanes with Bis(phosphino)borate Copper(I) ComplexCu

MANKAD, N.P.; PETERS, J. C.

MD

PPh2B

PCu NH2Mes

t-Bu2

t-Bu2

N2CR2

- NH2Mes

[Ph2BPt-Bu 2] Cu N N CR2

or

CR2Cu[Ph2BPt-Bu 2]

or

Cu NN

CR2

CR2

[Ph2BPt-Bu 2]

B

Chem. Commun. 1061 10632008 -, , 9 ,

Cu-Catalyzed Silylation of Cyclopropenes with (Trifluoromethyl)trimethylsilaneCu

FORDYCE, E. A. F.; WANG, Y.; LUEBBERS, T.; LAM, H. W.

MD

R2R1

R3

+ TMSCF3

Cu(acac)2 (5 mol%)dppe (5 mol%)

THF, r.t.

R2R1

R3TMS

10 examples

66-99% yield

Chem. Commun. 1124 11262008 -, , 9 ,

Preparation of Neutral Organocopper(III) ComplexesCu

BARTHOLOMEW, E. R.; BERTZ, S. H.; COPE, S.; DORTON, D. C.; MURPHY, M.; OGLE, G. A.

MD

(CH3)2CuILi.LiI1) L

2) Et-ICuIII

CH3

CH3

LCH3CH2

THF-d8, -100°C

10 complexes

Chem. Commun. 1176 11772008 -, , 10 ,

Isomerization of Alkyl Grignard Reagents by Fe-Cu Cooperative CatalysisCu

SHIRAKAWA, E.; IKEDA, D.; YAMAGUSHI, S.; HAYASHI, T.

MD

R

MgX

FeCl3 (2.5 mol%)

CuBr (5 mol%)

PBu3 (10 mol%)

THF, -25°C

RMgX

ER

E'

E = ClSiH2Ph, PhCHO, CO2R = Et, Bu, PhX = Br, Cl isomerization ration > 99%

76-82% yield

Fe

Chem. Commun. 1214 12162008 -, , 10 ,

44


Cu-Catalyzed Carbomagnesiation with Grignard ReagentsCu

TODO, H.; TERAO, J.; WATANABE, H.; KUNIYASU, H.; KAMBE, N.

MD

R'

R'

R'

RMgXLi2CuCl4 (1 mol%)

THF, 25°C

R'

R'

MgXR

RC

MgX

R'8 examples

Mg

Chem. Commun. 1332 13342008 -, , 11 ,

Cu-Mediated Tandem CO Insertion and Annulation of 1,4-Dilithio-1,3-dienesCu

LUO, Q.; WANG, C.; ZHANG, W.-X.; XI, Z.

MD

Li

LiR2

R3

R1

R4

1) 2 CuCl2) CO (1 atm)

2 tBuOOtBu

O

R1

R2

R3

R4

and/or

O O

R1 R1

R2 R2

R4

R3

R4

R3

8 examples

Li

Chem. Commun. 1593 15952008 -, , 13 ,

Cu-Catalyzed Conjugate Addition of Arylboronic Acids to AlkynoatesCu

YAMAMOTO, Y.; KIRAI, N.; HARADA, Y.

MD

+B(OH)2

R1

R2 CO2R3

CuOAc (1-10 mol%)

MeOH, r.t.

R2 CO2R3

R1

20 examples

60-97% yield

R1 = Me, Cl, Br, I, OMe, CHO, Ac, CO2Et, NO2

R2 = Alkyl, Aryl

Chem. Commun. 2010 20122008 -, , 17 ,

Efficient Addition of Alcohols, Amines and Phenol to Unactivated Alkenes Cu

ZHANG, X.; CORMA, A.

BS

AlkenesCatalystAu(III) + CuCl2

Ethers

Secondary Amines

Ethers

Alcohols

Phenol

Primary amines

AuPd

Dalton Trans 397 4032008 -, , 3 ,

45


Ternary Metal(II) Complexes of Edda and an Intercalating ligandCu

HEE NG C.; KONG, K. C.; VON, S. T.; BALRAJ, P.; JENSEN, P.; THIRTHAGIRI,E.; HAMADA, H.; CHIKIRA, M.

BS

N

N

M

O

NH

NH

O

O

O

M = Cu, Co, Zn,

CoZnNi

Dalton Trans 447 4542008 -, , 4 ,

Tetranuclear Cu(II) PhosphonatesCu

DNA cleavage.

CHANDRASEKHAR, V.; AZHAKAR,R.; SENAPATI, T.; THILAGAR, P.; GHOSH, S.; VERMA, S.; BOOMISHANKAR,R.;STEINER, A.; KÖGERLER, P.

BSDalton Trans 1150 11602008 -, , 8 ,

Highly Efficient Copper-Mediated Atom-Transfer Radical Addition (ATRA) Cu

Addition of polybrominated compounds to alkenes in the presence of AIBN.

ECKENHOFF, W. T.; GARRITY, S. T.; PINTAUER, T.

BS

CuI(TPMA)Br [TPMA = tris(2-pyridylmethyl)amine]

Eur. J. Inorg. Chem. 563 5712008 -, , 4 ,

Trinuclear Copper-PHI Complex Derived from L-Histi dineCu

Cu3(PHI)(N3)x exhobits biomimetic monooxygenase activity towards phenolic substrates.

GULLOTTI, M.; SANTAGOSTINI, L.; PAGLIARIN, R.; PALAVICINI, S.; CASELLA, L.; MONZANI, E.; ZOPPELLARO, G.

BSEur. J. Inorg. Chem. 2081 20892008 -, , 12 ,

46


New Copper(II) Tetraazamacrocycle Complexes for Oxidation of PhenolCu

BANSAL, V. P.; KUMAR, R.; PRASAD, R.; PRASAD, S.; NIRAJ.

PLA

NH HN

NH HN

L =

OH H2O2

LCuCl2

OHHO

ortho : para up to 93:7

J. Mol. Catal. A 69 762008 284 -, , 1-2,

Pd-free Sonogashira Coupling of Alkynes with Aryl Halides and Arylboronic AcidsCu

MAO, J.; GUO, J.; JI, S.-J.

PLA

R

R = Aryl, alkyl

+ ArXX = B(OH)2, 14 - 26 %, 6 examples

CuBr, rac-BINOL

Cs2CO3, DMFR Ar

X = I, Br, 23 - 87 %, 10 examplesB

J. Mol. Catal. A 85 882008 284 -, , 1-2,

Zeolite Encapsulated Copper Complexes as Oxidation Catalysts Cu

Encapsulation provides better catalytic activity and lifetime.

SALAVATI-NIASARI, M.

PLA

X

N N

X

R R

Cu2+O-

O-

O-

X = NH, O, S

Na+Na+

Cu([R]2-N2X2)]2+-NaY =

Cu([R]2-N2X2)]2+-NaY

TBHPCOCH3

selectivity up tp 97 %

J. Mol. Catal. A 97 1072008 284 -, , 1-2,

Cu-exchanged Heteropoly Acid as Catalyst for Alkene Cyclopropanation Cu

Reusable catalyst

YADAV, J.S.; SUBBA REDDY, B. V.; PURNIMA, K. V.; NAGAIAH, K.; LINGAIAH, N.

PLA

R1

+ N2CHCO2EtCu-TPA (10 %)

CH2Cl2, R.T.R3

R2

R1

R3

R2

CO2Et

12 examples 80-95 %, trans:cis up to 2.4:1

Cu-TPA:Cu1.5PW12O40 Cu-exchanged

phosphotungstenic acid

W

J. Mol. Catal. A 36 402008 285 -, , 1-2,

47


Zeolite Encapsulated Copper Complexes as Catalysts for Cyclohexane Oxidation Cu

Encapsulation of Cu-complexes gives better catalytic activity and affords reusable catalysts.

SALAVATI-NIASARI, M.; SOBHANI, A.

PLA

H2O2

[ML]-NaY

M = Cu, Mn, Co, Ni

+

O OH

O-

O-

O-

Na+Na+

[ML]-NaY =

O

NHN NH

N

OM(II)

O O

up to 82.5:17.5 selectivity

MnCoNi

J. Mol. Catal. A 58 672008 285 -, , 1-2,

Cu-Based Catalyst System for the Reactions of Alcohols with Aryl HalidesCu

ALTMAN, R. A.; SHAFIR, A.; CHOI, A.; LICHTOR, P. A.; BUCHWALD, S. L.

BS

X

R1

+ HOR2

OR2

R1

L =N

N

CuI ( 0.05 eq.), L (0.1 eq.)

Cs2CO3, Toluene, 80-130°C, 12-30 h

X = I, Br. R1 = Cl, Br, OMe, CF3 .R2 = Alkyl, Benzyl, Allyl, Propargyl.72-99 %

J. Org. Chem. 284 2862008 73 -, , 1 ,

Conjugation of Nucleosides and OligonucleotidesCu

JAWALEKAR, A. M.; MEEUWENOORD, N.; CREMERS, J. G. O.; OVERKLEEFT H. S.; VAN DER MAREL, G. A.; RUTJES,F. P. J. T.; VAN DELFT, F. L.

BS

OH

A

HO O

O

HO

RN3 (1 eq.), Cu-wire

CH3CN, H2O OH

A

HO O

O

HO

N

N

N

R

yield > 92%

J. Org. Chem. 287 2902008 73 -, , 1 ,

Enantioselective SN2' Allylic Alkylation Catalyzed by Copper-Carbene ComplexesCu

SEO, H.; HIRSCH-WEIL, D.M.; ABBOUD, K. A.; HONG, S.

BS

OPiv

C (0.03 eq.), n-HexMgBr (1.5 eq.)

Et2O, 0°C, 1 h, 91%

n-Hex

+

n-Hex

(SN2)(SN2')

SN2'/SN2 = 85/15

C =N N

Cy CyCuCl

J. Org. Chem. 1983 19862008 73 -, , 5 ,

48


Validation of the Copper(I)-Catalyzed Azide-Alkyne Coupling in Ionic LiquidsCu

MARRA, A.; VECCHI, A.; CHIAPPE, C.; MELAI, B.; DONDONI, A.

BS

Sugar + N3

Sugarionic liquid, 80°C, 16 h

Sugar N

Sugar

up to 95% yieldCuI (0.5 eq.), i-Pr2EtN (5 eq.)

J. Org. Chem. 2458 24612008 73 -, , 6 ,

Ligandless Microwave-Assisted Pd/Cu-Cat. Arylation of OxazolesCu

BESSELIÈVRE, F.; MAHUTEAU-BETZER, F.; GRIERSON, D. S.; PIGUEL, S.

BS

N

OAr1

Ar2Br (1.2 eq.), Pd(OAc)2 (0.05 eq.), CuI (1 eq.)

K2CO3 (2 eq.), DMF, µW, 150°C 4-15 min.

N

OAr1 Ar2

63-81%

Pd

J. Org. Chem. 3278 32802008 73 -, , 7 ,

Intramolecular C-Arylation of Benzylic CarbonCu

SALCEDO, A.; NEUVILLE, L.; ZHU, J.

BS

NH

N

O

O

I

R1

R2I 1) Cu(I) cat.

2) Pd(0) cat. N

O

N

R2O

R1

Ugi 4CR Adduct up to 60% yield

Pd

J. Org. Chem. 3600 36032008 73 -, , 9 ,

Multicomponent One-Pot Reaction of Azide and Alkyne Mediated by CuI/NBSCu

LI, L.; ZHANG, G.; ZHU, A.; ZHANG, L.

BS

HS P

SPh

O

OO

NH

O

OO

HON3

+CuI (1 eq.), NBS (1 eq.) HS P

SPh

O

OO

NH

O

O

N

N

N

IO

OO

HO

90 %THF, RT, 3 h

J. Org. Chem. 3630 36332008 73 -, , 9 ,

49


Synthesis of Sugar Triazoles with 1,3-CycloadditionCu

The synthesized sugar triazoles were evaluated for their antitubercular activity.

SINGH, B. K.; YADAV, A. K.; KUMAR, B.; GAIKWAD, A.; SINHA, S. K.; CHATURVEDI,V.; TRIPATHI, R. P.

LS

OO

OMe

Me

N3

OBzlO

N3

OO

Me Me

OMe

ON3

OHOH

OMe

oror

ON

R2R3

R1

NN

RR H

CuSO4 (2 mol %)/sodium ascorbate (5 mol %)/ t-BuOH/H2O (1:1), 30°C, 2.5 to 18 h

(1 eq).

R = Ph, CH2-OH, Bn, alkyl15 Examples

Yield = 60 - 94%

Organometallics 1153 11622008 343 -, , ,

Copper-Catalyzed Binaphtol SynthesisCu

YAN, P.; SUGIYAMA, Y.; TAKAHASHI, Y.; KINEMUCHI, H.; TEMMA, T.; HABAUE, S.

LE

OHR1

R2 R3

CO2PhHO

+

CuCl-(S)Phbox 0.2 eq.Yb(OTf)3 0.1 eq.

O2, THF, rt

OHR1

R2 R3

CO2PhHO

74-99%9-86% ee

Tetrahedron 4325 43312008 64 -, , 19 ,

Copper-Catalyzed Suzuki CouplingCu

The use of iodine as an additive allow the coupling of aryl chlorides

MAO, J.; GUO, J.; FANG, F.; JI, S.-J.

LE

Ar1I Ar2B(OH)2+Cu powder

PEG-400K2CO3

Ar1 Ar2 77-99%

B

Tetrahedron 3905 39112008 64 -, , 18 ,

Copper-Catalyzed Coupling of Aryl Halides with NH-HeterocyclesCu

The coupling of other NH-heterocycles is also described

XI, Z.; LIU, F.; ZHOU, Y.; CHEN, W.

LE

ArX

HetArXor

CuI 0.1 eq, L 0.1 eq.

K2CO3, DMF, 110°CNHN+

NNAr

NNArHet

or

77-98%

65-99%

N

O O

N

L =

Tetrahedron 4254 42592008 64 -, , 19 ,

50


N-Arylation of Pyrazole Catalyzed by a Trinuclear Copper ComplexCu

Other azoles, amides and phenols are also coupled

TUBARO, C.; BIFFIS, A.; SCATTOLIN, E.; BASATO, M.

LE

R X NNH

+[Cu] 3mol%

Cs2CO3, DMSO100°C, 24h

NNR

16-93%

Tetrahedron 4187 41952008 64 -, , 19 ,

Asymmetric 1,4-Conjugate Additions of Diethylzinc to ChalconesCu

BIRADAR, D. B.; GAU, H.-M.

TJ

O

R1 R2

O

R1 R2 PPh2

N OH

BnPh

Ph5 mol% Ligand

5 mol% Cu(acac)2

Hex/Et2O-40 °C, 16 h 14 examples

Yield >89%ee 81-97%

Ligand =

+ Et2Zn


Amidation of Allylic and Benzylic AcetatesCu

POWELL, D. A.; PELLETIER, G.

TJ

OAcR1

R2

NH

R3 SR4

O ONR3

SR4

O OR2

R1+

5 mol% Cu(OTf)210 mol% t-BuOOAc

ClCH2CH2Cl25-60 °C

14 examples40-93%


A Tandem Ferrier and Click ReactionCu

YADAV, J. S.; REDDY, B. V. S.; CHARY, D. N.; REDDY, CH. S.

TJ

O

ORRO

ROO

RO

RON

NNRO

RO

RON

NNR

5 mol% Cu(OTf)210 mol% Cu powder

TMSN3, MeCN, rt

+αααα ββββ

R α/β = 3:2 to 9:165-85% Yield


51


Synthesis of Polyfonctionalized BenzofuransCu

SAKAI, N.; UCHIDA, N.; KONAKAHARA, T.

TJ

R2CHO

OH

NH

R R

Me3Si R1

+

O R1

NR

R5% Cu(OTf)2

5% CuCl

DMAPCH3CN, reflux, 6 h 11 examples

22-91%

R = allyl, -(CH2)5

R1 = H, Ph, C6H13

R2 = H, Me, NO2, Br


3D Coordination Network PolymerAg

RICHARDS, P. I.; BICKLEY, J. F.; BOOMISHANKAR, R.; STEINER, A.

BJL

PN

PNP

N NR2

R2N

R2N NR2

NR2

R2N

R:Ag(I)

3D coordination network

Chem. Commun. 1656 16582008 -, , 14 ,

Selective Ag+/Cu2+ Separation by AdsorptionAg

LAM, K. F.; CHEN, X.; FONG, C. M.; YEUNG, K. L.

BJL

MCM-41 adsorbents functionnalized by amine groups were prepared and used for silver adsorption from solution containing copper.

Cu

Chem. Commun. 2034 20362008 -, , 17 ,

Synthesis of 1,2-Dihydroisoquinoline DerivativesAg

DING, Q.; YU, X;; WU, J.

TJ

CHO1. 2-5 mol% AgOTf

10 mol% proline 4A MS, EtOH, rt

2. NaBH4

15 examplestrace-96%

R1

+ R2-NH2N

R1

R2

R1 = Ph, p-MeOPh, cyclopropylR2 = Ar, n-Hexyl


52


Ketene Aminals and Tetraaminoallenes: a New Class of LigandsAu

FÜRSTNER, A.; ALCARAZO, M.; GODDARD, R.; LEHNMANN, C. W.

CY

N N

N N

AuPPh3

+SbF6–

AuCl(PPh3), NaSbF6, THF

NMe2

NMe2Me2N

Me2N

Me2N NMe2

Me2N NMe2

+

AuPPh3

SbF6–

AuCl(PPh3), NaSbF6, THF

Angew. Chem. Int. Ed. 3210 32142008 47 -, , 17 ,

Au-Catalyzed Synthesis of Pyrrolo[1,2-a]quinolines in waterAu

LIU, X.-Y.; CHE, C.-M.

CY

NH

OPh

N

OPh

+

(4 equiv)

Au[P(tBu)2(o-biphenyl)]Cl (5 mol%),AgSbF6 (5 mol%), H2O, 75 ºC, 30h

93%

19 examples

Angew. Chem. Int. Ed. 3805 38102008 47 -, , 20 ,

Aerobic Oxidation of AlcoholsAu

The Au-Pt clusters present higher activity and selectivity than the single metal clusters

MIYAMURA, H.; MATSUBARA, R.; SHU KOBAYASHI, S.

BJL

OH

R2R1

O

R2R1

Au/Pt (1 mol%)

rt, O2, BTF/H2O, rt

Au/Pt: gold/platinum alloyed bimetallic clusters supported on a cross-linked polystyrene derivative.67-99%

Pt

Chem. Commun. 2031 20332008 -, , 17 ,

Stable Gold Nanoparticle–DNA ConjugatesAu

SHARMA, J.; CHHABRA, R.; YAN, H.; LIU, Y.

BJL

HN C

S

SRNH2R +

SCS pH 9.0

HN C

S

SR

Colloidal solution of Au nanoparticles

Chem. Commun. 2140 21422008 -, , 18 ,

53


Elucidating Phenol Mechanism by Labeling ExperimentsAu

HASHMI, A. S. K.; RUDOLPH, M.; SIEHL, H.-U.; TANAKA, M.; BATS, J. W.; FREY, W.

MF

O X

R2

R1

DO

XD

R1

R2

X

R1

R2

OH

AuIII Cat.

Chem. Eur. J. 3703 37082008 14 -, , 12 ,

1,2-Alkyl Migration Catalyzed by Au or Pt CatalystsAu

CRONE, B.; KIRSCH, S. F.

MF

RM

R

OX

M

R

O

R- X+

Au / Pt

Pt

Chem. Eur. J. 3514 35222008 14 -, , 12 ,

Dinuclear Au(I) Complexes Linked by Diethynylpyridine GroupsAu

LI, P.; AHRENS, B.; BOND, A. D.; DAVIES, J. E.; KOENTJORO, O. F.; RAITHBY, P. R.; TEAT, S. J.

BS

R3PAu X

2

R = Ph, Cy.X = 2,5- or 2,6 or 2,5'-pyridine, 2,6'-bipyridine

Dalton Trans 1635 16462008 -, , 12 ,

Catalytic Properties of Au(I) Complexes with 4-Substituted PyridinesAu

First activation of bromoarenes with Au(I) in cross-coupling reaction with boronic acids

LIN, J. C. Y.; TANG, S. S.; SEKHAR VASAM, C.; YOU, W. C.; HO, T. W.; HUANG, C. H.; SUN, B. J.; HUANG, C. Y.; LEE, C.S.; HWANG, W. S.; CHANG, A. H. H.; LIN, I. J. B.

MVI

Br

CH3

B(OH)2 N NMe2Au

H3C2

[AuCl2)]

DMF, K2CO3, RT or 130°C

air or N2

Inorg. Chem. 2543 25512008 47 -, , 7 ,

54


Annulation of Enynes and AlkynesAu

GORIN, D. J.; WATSON, I. D. G.; TOSTE, F. D.

CJM

Ar

R1

+

OPiv

Ar

R1R1

RAgOTf 5%(ArO)3PAuCl 5%

CH2Cl2, rt

AgSbF6 5%(ArO)3PAuCl 5%

CH2Cl2, rt

J. Am. Chem. Soc. 3736 37372008 130 -, , 12 ,

Cycloisomerization of 1,5-AllenynesAu

CHEONG, P. H.-Y.; MORGANELLI, P.; LUZUNG, M. R.; HOUK, K. N.; TOSTE, F. D.

CJM

•

R3

R1

R2 Ph3PAu

AuPPh3DFT studies

R3

R1

R2

J. Am. Chem. Soc. 4517 45262008 130 -, , 13 ,

Propargylic Pivalates RearrangementsAu

LI, G.; ZHANG, G.; ZHANG, L.

CJM

OPiv

R2iPrAuNTf2 5%

DCE, 80 °CR

OPivR2

R1

J. Am. Chem. Soc. 3740 37412008 130 -, , 12 ,

Double Intramolecular Hydroalkoxylations.Au

Other examples with alkynyl di-phenols.

ZHANG, Y.; XUE, J.; XIN, Z.; XIE, Z.; LI, Y.

MJ

OH

( )m

( )n

OH

OO OO

O

O

( )n

( )n

"Au" (cat.)

CH2Cl2, rt

m = 1, n = 0: 75%m = 1, n = 1: 52% 34%m = 1, n = 1: 84%

Ph3PAuCl (0.02 equiv.)AgOTf (0.02 equiv.)

25-30 minPh3PAuCl (0.1 equiv.)

AgOTf (0.1 equiv.)4 d

m = 1, n = 1: 52%m = 1, n = 1: 72%

Synlett 940 9442008 -, , 6 ,

55


Cyclization.Au

11 examples. Lower yields using In and Zn catalysts.

YEOM, H.-S.; KIM, S.; SHIN, S.

MJ

NO

Ph

NOH

Ph

catalyst (0.05 eq.)

CH2Cl2, rt, 30 min

Au(IMes)OTf: 96%AgOTf: 85%

Ag

Synlett 924 9282008 -, , 6 ,

Diastereoselective Addition of Silyl Substituted Crotylzinc to Carbonyl CompoundsZn

HELM, M. D. H.; MAYER, P.; KNOCHEL, P.

MVI

SiR3

Me

ZnCl.LiCl

O

RSRLSiR3

RL

OHRS

THF, -78°C

High yieldsHigh diastereoselectivities

Si

Chem. Commun. 1916 19172008 -, , 16 ,

Catalyst Self-Adaptation in Conjugate Addition to Nitroalkenes and NitroacrylatesZn

Tropos ligands more efficient than the atropos analogues

WAKABAYASHI, K.; AIKAWA, K.; KAWAUCHI, S.; MIKAMI, K.

MVI

O

OP

Ph

PhPh

NO2

Et

Et2ZnNO2RMe3Al

EtO2C

NO2

Me+

[2% Cu(OTf)2 + 4% L]R = CO2Et R = Ph

LAl

J. Am. Chem. Soc. 5012 50132008 130 -, , 15 ,

Enantioselective Addition of Arylzinc Reagents under Microwave ConditionsZn

Acceleration of both formation and addition of arylzinc species under these conditions

BRAGA, A. L.; PAIXAO, M. W.; WESTERMANN, B.; SCHNEIDER, P. H.; WESSJOHANN, L. A.

LE

Ar1B(OH)2 Et2Zn+

L (10 mol%)

Ar2CHO

Toluene, MW (300W) Ar1 Ar2

OH

88-98 %

70-98 % ee

L =

N

Tr

OH

PhPhB

J. Org. Chem. 2879 28822008 73 -, , 7 ,

56


Synthesis of TrimethylsilylalkynesZn

Allows the silylation of functionnalized alkynes

RAHAIM, R. J.; SHAW, J. T.

LE

R H R SiMe3TMSOTf 1.5eq., NEt3 1.5 eq.

Zn(OTf)2 cat.

CH2Cl2, rt81-100%

J. Org. Chem. 2912 29152008 73 -, , 7 ,

Preparation of N-Sulfonyl and N-SulfinyliminesZn

FAN, R.; PU, D.; WEN, F.; YE, Y.; WANG, X.

LE

R1CHO R2SH2N

O X

X = O or :

+PhCH2Br, Zn

THF, rt

R2SN

O X

R1

55-98 %

J. Org. Chem. 3623 36252008 73 -, , 9 ,

Synthesis of Furan Derivatives by Addition of zinc Reagents to 2-Alkynyl AldehydesZn

CHAI, Z.; XIE, Z.-F.; LIU, X.-Y.; ZHAO, G.; WANG, J.-D.

LE

CHO

R1

RZnR', L*rt then reflux

O

R1

R

or O

R1

R

For aromatic cycles For cycloalkenes

59-83 %36-97 %ee

70-75%

NHO

O

O

O

O

Ph

Ph

O Ph

O Ph2

L =

J. Org. Chem. 2947 29502008 73 -, , 7 ,

Mechanism of the Aqueous Barbier Allylation ReactionZn

DAM, J. H.; FRISTRUP, P.; MADSEN, R.

LE

Ar

O

H/DBr+ Met

H2O Ar

OHD/H

Met = Zn, Sn, Sb, Bi, Mg

InSnSbBiMg

J. Org. Chem. 3228 32352008 73 -, , 8 ,

57


From Bromohydrins to Ketones Through Zinc-Mediated 1,2-MigrationZn

LI, L.; CAI, P.; GUO, Q.; XUE, S.

LE

OHPhAc

( )n

O

Ph

( )n

Et2Zn 0.6 eq.

CH2Cl2, rt

85-98 %

J. Org. Chem. 3516 35222008 73 -, , 9 ,

Carbometallation of Unactivated Alkenes by Zinc Enolate DerivativesZn

Prospective article (89 references).

PEREZ-LUNA, A.; BOTUHA, C.; CHEMLA, F.

CB

[Zn]

EWG

[Zn]

EWG

Inter or Intra Carbometallation reaction

Stabilized zinc enolate Non stabilizedalkylzinc reagent

New J. Chem. 594 6062008 32 -, , 4 ,

Regioselective Transfer of Prenyl Anion.Zn

Application to the synthesis of (+/-)-Shikonin.

XU, D.-F.; ZHAO, L.-M.; MAO, Z.-Q.; LI, S.-S.

CB

O O

O OCHO

OH O

OH O OH

R

OH

R

R

OH

94% 85%

HMPAor NMP

130°C / 24h

Br

Zn dust

LiClO4

THF

BrZn

(+/-)-Shikonine 80%

CH3CN-H2O

ElectrolyzedPt/3V

Org. Prep. Proc. Int. 93 962008 40 -, , 1 ,

Three-Component Approach to the Synthesis of αααα,αααα-Disubstituted AminesZn

Reactions are conducte.d under Barbier-like conditions using simple organic halides and zinc dust

SENGMANY, S.; LE GALL, E.; TROUPEL, M.

OS

Br

NH2

H

ON

79%

Zn

MeCN, 1 h.+ +

Synlett 1031 10352008 -, , 7 ,

58


Synthesis and Functionalization of PolyynesZn

Practical synthetic procedures via alkylidene carbenoids.

LUU, T.; MORISAKI, Y.; TYKWINSKI, R.R.

GJ

I OCH3

H

BrBr

Ph

ZnClPhb) ZnCl2

(Ph3P)4Pd

OCH3Ph

a) BuLi (2 equiv)toluene

80%

LiPd

Synthesis 1158 11622008 -, , 7 ,

Enantioselective Addition of Organozinc Reagents to Ketones.Zn

Use of nanosize isoborneol ligands.

FORRAT, V.J.; RAMON, D.J.; YUS, M.

CB

Ar

O

RR'2Zn

Ar

HO

up to 99% ee

5 mol% L* =

+

R'

PhCH3 25°C / 2-7 dR

Ti(O-iPr)4 (1.1 equiv)

HNNHSO2

SO2OH

S-Frechet-dendron

R' = Me, Et, PhR = Me, Et

Ti


Enantioselective Diethylzinc Addition to Aldehydes.Zn

Use of β-hydrosalicylhydrazones ligands.PARROT II, R.W.; DORE, D.D.; CHANDRASHEKAR, S.P.; BENTLEY, J.T.; MORGAN, B.S.; HITCHCOCK, S.R.

CB

Toluene / 25°C / 18h

R

O

H

Et2Zn

R

OH

84-92% ee10 mol% L* =

+

EtHO

NN

OHPh

Me

R1

R2

R3

R4R

R = Ar, CH=CHPh

(3 equiv)


Microwave-assisted Enantioselective Diethylzinc Addition to Aromatic Aldehydes.Zn

Catalysis in the presence of chiral aminonaphtols.

SZATMARI, I.; SILLANPÄÄ, R.; FÜLÖP, F.

CB

(2.5 equiv)

X

H

O

X

Et

X

Et

OH OH

10 mol% L* =ee up to 92%

+Et2Zn

OH

Ph NR

α-Naphtyl

OH

Ph NR

β-Naphtyl

or

Toluene


59


Hydroxyamide-catalyzed Enantioselective Diethylzinc Addition to Benzaldehyde.Zn

DE LA CASAS ENGEL, T.; MAROTO, B.L.; MARTINEZ, A.G.; DE LA MOYA CERERO, S.

CB

(2 equiv)

H

O

Et

OH

5 mol% L* =48-91% ee

Et2ZnHexane / rt / 5h

+

O N

R

An n = 1 or 2


Zn-Mediated Rh-Catalyzed αααα-Trifluoromethylation of KetonesZn

Mechanism of α-trifluoromethylation is proposed.SATO, K.; YUKI, T.; TARUI, A.; OMOTE, M.; KUMADAKI, I.; ANDO, A.

CC

Me3SiO

R R"

R'

RCF3

R' R"

Oi) ZnEt2 (1 eq), 0°C

ii) RhCl(PPh3)3 (4 mol%) CF3I, DME, rt

Yields = 23 - 84%

Rh


Asymmetric Simmons-Smith Reaction of Allylic Alcohols.Al

Authors propose that the bifunctional character of the catalytic system is responsible for good catalytic performances.

SHITAMA, H.; KATSUKI, T.

GR

R'

R OHAlR2X/L*

ZnEt2 (2eq)CH2I2 (2eq)

R'

R OH**

NH N

OH HO

Ph Ph

L*:

8 examplesquantitative yields

ee up to 95 %

Zn

Angew. Chem. Int. Ed. 2450 24532008 47 -, , 13 ,

Synthesis and Characterization of Aluminium and Zinc ComplexesAl

The synthesis of complexes is supported by pyridine-based N,N,N-chelate ligands. The catalysis of these complexes inεCHAI, Z.-Y.; ZHANG, C.; WANG, Z.-X.

LS

N N

NPh N

Me3Si

Al

R Cl

R = Me, Et N PPh2Ph2P

Me3SiN

NSiMe3Al

EtEt

4 steps, yield = 25%

3 steps, yield = 30%


60


Reactivity of Stable Silylenes toward Terminal AlkynesSi

The reaction leading to 1 is autocatalyzed by small amounts of 1YAO, S.; VAN WÜLLEN, C.; SUN, X.-Y.; DRIESS, M.

EJ

SiN

N

R

R

H

R'Si

N

N

R

R

SiN

N

R

R

H

R'

R' = H, PhCH CR'

hexane, rt

CH CR'

hexane

R = 2,6-iPr2C6H3

- 78°C1 2

12 82-93%

82-85%

Angew. Chem. Int. Ed. 3250 32532008 47 -, , 17 ,

Highly Substituted beta-Hydroxy-gamma-Lactams From beta-Silyloxy HomoenolatesSi

LETTAN, II, R. B.; WOODWARD, C. C.; SCHEIDT, K. A.

BN

NMe

Me

O

Me

Li

PhO TMS

LDA

THFN

Me

Me

O

Me

PhPh OH

HNP(O)Ph2

NMeMe

Me

O

TMS Ph

O Ph H

NP(O)Ph2Li

Angew. Chem. Int. Ed. 2294 22972008 47 -, , 12 ,

Imine CinnamylationSi

HUBER, J. D.; PERL, N. R.; LEIGHTON, J. L.

BN

NH

SiO

ClMe

Ph Ph

NH

SiO

ClMe

PhPh H Ph

NR

Ph

NHR

PhRu-2

R = CH2Ar, anti/syn > 20:1, 96% eeR = Ar, anti/syn = 1:7, 96% ee

Ru

Angew. Chem. Int. Ed. 3037 30392008 47 -, , 16 ,

Catalytic Asymmetric Silaboration of Acyclic Unsaturated Carbonyl CompoundsSi

WALTER, C.; OESTREICH, M.

BN

EtO

Bun

O

EtO

Bun

O

SiMe2Ph

[Rh(cod)2]OTf (5 mol%)(R)-BINAP (10 mol%)

Me2PhSi-Bpin

Et3N, dioxane/H2O (10:1)50 °C

55%, 99% ee

RhB

Angew. Chem. Int. Ed. 3818 38202008 47 -, , 20 ,

61


Vinyl Silanes From Aldehydes via a Metalation–Peterson SequenceSi

MCNULTY, J.; DAS, P.

BN

TMS Cl

TMS

TMS Li

TMS PhCHO TMSsBuLi

THF, -78 °C

E:Z > 9:1, 80%

Li

Chem. Commun. 1244 12452008 -, , 10 ,

Palladium-Catalysed Silaboration Reaction of Terminal AlkynesSi

Stereoselective access to the E isomer is also possible

OHMURA, T.; OSHIMA, K.; SUGINOME, M.

BN

BO

OMe

Me

MeMe

SiMe

MeCl C6H13

(PrOi)Me2Si

C6H13

B(pin)

(η3-allyl)PdCl(PPh)3

(1 mol%)

toluene, rt, 1h

then iPrOH, pyr Z

PdB

Chem. Commun. 1416 14182008 -, , 12 ,

Stereoelective Allylation of Carbonyl Compounds With Silyl-Substituted CrotylzincSi

Trapping with aldehydes was also studied

HELM, M. D.; MAYER, P.; KNOCHEL, P.

BN

MeTMS

Cl

Cl MeTMS

Me

TMSZnCl,LiCl

Zn, LiCl

THF, 25 °C18h

Zn

Chem. Commun. 1916 19172008 -, , 16 ,

A Novel Silyloxy Allenolate in The Reaction of Lithiated Diazoesters with AcylsilanesSi

GALLIFORD, C. V.; SCHEIDT, K. A.

BN

Ph

O

Li N2

CO2EtTMS

Ph

O

TMS

CO2Et

N2

Li -N2

Ph

O

CO2Et

COEt

OLi

Ph

TMSO H2O

Li

Chem. Commun. 1926 19282008 -, , 16 ,

62


Claisen rearrangement/intramolecular hydrosilation approach to medium-ring ethers.Si

MAK, S. Y. F.; CURTIS, N. R.; PAYNE, A. N.; CONGREVE, M. S.; WILDSMITH, A. J.; FRANCIS, C. L.; DAVIES, J. E.;PASCU, S. I.; BURTON, J. W.; HOLMES, A. B.

BN

OO

Et

OTPSSiH

MeMe

OHO

Et

OTPS

HO

OBr Cl

[RhCl(Ph3P)3], THF, rflx

then H2O2, KOH

dr up to 12.8:1 (+)-obtusenyne

Rh

Chem. Eur. J. 2867 28852008 14 -, , 9 ,

Silylene and Germylene Intermediates from Silole and Germole DianionsSi

This mechanism was supported by experimental data and theoretical calculations

TOULOKHONOVA, I.S.; TIMOKHIN, V.I.; BUNCK, D.N.; GUZEI, I.; WEST, R.; MÜLLER, T.

EJ

ELi2

PhPh

PhPh

NtButBuNTHF/rt

E:

PhPh

PhPh

NtButBuN

Li Li

NtButBuN

E

PhPh

PhPh

N

N

tBu

tBu

_

E = Si, Ge

55-63%

GeLi

Eur. J. Inorg. Chem. 2344 23492008 -, , 14 ,

Efficient Palladium-Catalysed Silylation Reaction of ArI Si

IIZUKA, M.; YOSHINORI, K.

BN

NC

I

SiMe2H

OTHP

NC

Me2Si

OH

Pd(OAc)2, pyridineLiCl, DMI, rt, 24hthen PTSA, MeOH 59%

Pd

Eur. J. Org. Chem. 1161 11632008 -, , 7 ,

Silylene Equivalents And Alkyne: Expeditive Access to 2,4-Disubstituted SilolesSi

OHMURA, T.; MASUDA, K.; SUGINOME, M.

BN

BO

OMe

Me

MeMe

SiMe

MeEt2N C6H13

SiMe2

C6H13

C6H13Pd(dba)2 (1 mol%)

P(t-Bu)2(2-biphenyl) (1.2 mol%)

toluene, rt74%

PdB

J. Am. Chem. Soc. 1526 15272008 130 -, , 5 ,

63


General Rhodium-Catalyzed Asymmetric Alkynylation ReactionSi

The sterically bulky substituents on Si and P are required to avoid alkyne dimerization

NISHIMURA, T.; GUO, X.-X.; UCHIYAMA, N.; KATOH, T.; HAYASHI, T.

BN

O

O PAr2

O

O

PAr2 OMetBu

tBu

Ph Me

O

TIPS

Ph

O Me

TIPS

[Rh(µ-OAc)(C2H4)2]2 (5 mol% Rh)

(R)-DTBM-segphos (5.5 mol%)

Dioxane80 °C, 12h, 99%

(R)-DTBM-segphos

Ar =

Rh

J. Am. Chem. Soc. 1576 15772008 130 -, , 5 ,

Stereospecific Chromium-Promoted Silyl Cyclopropanation of Unsaturated AmidesSi

CONCELLON, J. M.; RODRIGUEZ-SOLLA, U.; MEJICA, C.; BLANCO, E. G.; GARCIA-GRANDA, S.; DIAZ, M. R.

BN

C5H11 CONMe2

TBS

C5H11 CONMe2

CrCl2Br2CHSitBuMe2

THF, rt

Cr

Org. Lett. 349 3522008 10 -, , 2 ,

Theoretical Studies of the Thermal Rearrangement of Silylene Me3SiSiHSi

The energy barrier for the CH insertion by the silylene are predicted to be 12.7 kcal/mol

BOO, B.H.; IM, S.; PARK, S.; LEE, S.

EJ

R

R M

R = tBuRC P

Et2OMP4C4R4

-70°C to rt

M = Ge, 43%

M = Sn, quantitative, but unstable compound


Complexes of Germanium (IV) Fluoride with Phosphane LigandsGe

Complexes have also been made between AsR3 and GeF4 or GeCl4DAVIS, M.F.; LEVASON, W.; REID, G.; WEBSTER, M.

EJ

GeF4(MeCN)2

PR3

CH2Cl2/rttrans-[GeF4(PR3)2]

R2P(CH2)2PR2

CH2Cl2/rtcis-[GeF4(R2P(CH2)2PR2)] 40 to 90%

PAs

Dalton Trans 2261 22692008 -, , 17 ,

64


Synthesis and Theoretical Studies of a Novel Organophosphorus Cage CompoundGe

DFT calculations support the reaction pathway

FRANCIS, M.D.; HITCHCOCK, P.B.; NIXON, J.F.; NYULASZI, L.

EJ

R

R M

R = tBuRC P

Et2OGeP4C4R4

-70°C to rt

M = Ge, 43%

M = Sn, quantitative, but unstable compound

SnP

Eur. J. Inorg. Chem. 1761 17662008 -, , 11 ,

Synthesis of Aluminogermanate NanotubesGe

Structural analogy with imigolite Al2SiO3(OH)4

LEVARD, C.; ROSE, J.; MASION, A.; DOELSCH, E.; BORSCHNECK, D.; OLIVI, L.; DOMINICI, C.; GRAUBY, O.; WOICIK,J.C.; BOTTERO, J.-Y

EJ

Et4-orthosilicate

Et4-orthogermanate/AlClO4

Ge-imigoliteNaOHrt/12h then 95°C/5d

Al

J. Am. Chem. Soc. 5862 58632008 130 -, , 18 ,

Hydrogermolysis Reactions Involving Germylated NitrilesGe

Compound 2 tBu3GeGePh3 could not be obtained due to the too large steric hindrance

AMADORUGE, M.L.; DIPASQUALE, A.G.; RHEINGOLD, A.L.; WEINERT, C.S.

EJ

R3GeClLiCH2CN

THFR3GeCH2CN

Ph3GeH

CH3CNR3Ge GePh3

R = Ph, iPr, tBu

-78°C to rt 85°C/2d62-70% 87-90%

1 2

1:

2: R = Ph, iPr

Li

J. Organomet. Chem. 1771 17782008 693 -, , 10 ,

Synthesis, Structure and Reactivity of OligogermanesGe

From 1, F3CSO3H, LiAlH 4 and again CH3CN and PhGeH3, oligogermanes are obtained

AMADORUGE, M.L.; GOLEN, J.A.; RHEINGOLD, A.L.; WEINERT, C.S.

EJ

Ph3GeNMe2

CH3CNPh3GeCH2CN

PhGeH3

CH3CN85°C/48h

PhGe(GePh3)3 85%

1

LiAl


65


Distannylation and Silastannylation of In situ Generated AllenesSn

WESQUET, A. O.; KAZMAIER, U.

LGE

RO

ROSnBu3

Bu3SnSnBu3

Bu3SnH, Pd(0)

Bu3SnH, Mo(0)

Bu3SnH, Pd(0)

Si

Angew. Chem. Int. Ed. 3050 30532008 47 -, , 16 ,

Oxidation of the Stannole DianionSn

HAGA, R.; SAITO, M.; YOSHIOKA, M.

LGE

Sn

Ph

Ph

Ph

Ph

Li Li

O2 (1.3 equiv.) 81 %

Li (quantitatif)

Sn

Ph

Ph

Ph

Ph

Li

Sn

Ph

Ph

Ph

Ph

Sn

Ph

Ph

Ph

Ph

Li

Li

Chem. Eur. J. 4068 40732008 14 -, , 13 ,

Reactivity of the Tin-Carbon Bond of an Almost Planar StanneneSn

Stannene 1, the X-ray crystal structure of which is reported, reacts with crotonaldehydes by a [2+4] cycloaddition.

FATAH, A.; AYOUBI, R.E.; GORNITZKA, H.; RANAIVONJATOVO, H.; ESCUDIÉ, J.

TT

CSn

O CHMe

H H

TipTip R2

iPr

iPr

iPr

Tip2SnF2 Tip2Sn = CR2

CH3CH=CH-CHOCR2 = Tip =

2 steps

1

tBu

tBu

Eur. J. Inorg. Chem. 2007 20132008 -, , 12 ,

Crotylation of Aldehyde by CrotyltinsSn

The reaction between aldehydes and crotyltins is highly dependant on the nature of aldehyde, metal salt and solvent

FARGEAS, V.; ZAMMATTIO, F.; CHRÉTIEN, J.-M.; BERTRAND, M.-J.; PARIS, M.; QUINTARD, J.-P.

LGE

SnBu3+ RCHO

Lewis acid

Solvent

R

OH

Z or E

R

OH

syn or antiLewis Acid : BF3.OEt2, InCl3, InBr3, CeCl3.7H2OSolvent : CH2Cl2, CH3CN

+

Simple Lewis acid assistance on the aldehyde = syn + ZTransmetallation before addition to the aldehyde = anti + E

CeIn

Eur. J. Org. Chem. 1681 16882008 -, , 10 ,

66


An Efficient Catalyst for Ring-Opening Polymerization of εεεε-CaprolactoneSn

1 catalyzes efficiently the polymerization of ε-caprolactone with low tin residues in the final products.POELMANS, K.; PINOIE, V.; VERBRUGGEN, I.; BIESEMANS, M.; DESHAYES, G.; DUQUESNE, E.; DELCOURT, C.;DEGÉE, P.; MILTNER, H.E.; DUBOIS, P.; WILLEM, R.

TT

O

OOH

P (CH2)11 SnCl3

O

(CH2)5-O-HCH3-CH2-CH2-Oncatalyst 1

1


Optically Active Organotin Compounds for Chiral PolystannanesSn

The chiral information of the myrtanyl group is transferred onto the polymer backbone.

BECKMANN, J.; DUTHIE, A.; GRASSMANN, M.; SEMISCH, A.

TT

SnR R

R2SnCl2 R2SnH2

i) LiAlH 4

ii) H2O

[(Ph3P)3RhCl] cat.

- H2 n

R = cis-Myr

R = trans-Myr


From Lead Selenide to Heterostructured NanocrystalsPb

PIETRYGA, J.M.; WERDER, D.J.; WILLIAMS, D.J.; CASSON, J.L.; SCHALLER, R.D.; KLIMOV, V.I.; HOLLINGSWORTH,J.A.

EJ

PbOOleic acid

Trioctylphosphine

PhOPh

lead selenide nanocrystals

150°C

205°C

Trioctylphosphine Se

J. Am. Chem. Soc. 4879 48852008 130 -, , 14 ,

Direct Conversion of Acetonides into DiacetatesBi

WU, .Q.-P.; ZHOU, M.-X.; XI, X.-D.; SONG, D.; WANG, Y.; LIU, H.-X.; LI, Y.-Z.; ZHANG, Q.-S.

CC

O

OO

O

O

RO

AcOAcO O

OAc

O

ROOAc

AcOAcO O

OAc

OAc

RO

AcO

AcOO

O

O

RO

Bi(OTf)3.xH2O(5 mol%),

Ac2O (3 eq),CH2Cl2, rt


Ac2O (3 eq),CH2Cl2, rt


Ac2O (3 eq),CH2Cl2, rt89% 85% 85%


67


Hydrosilylation Reactions Catalyzed by Copper, Silver, and Gold ComplexesRv

DIEZ-GONZALEZ, S.; NOLAN, S. P.

BN

Si

Acc. Chem. Res. 349 3582008 41 -, , 2 ,

Catalytic C-C, C-N, and C-O Ullmann-Type Coupling ReactionsRv

MONNIER, F.; TAILLEFER, M.

MF

UllmannBreakthroughR

X NuR

Nu

Enantioselectivity

Orthogonal Selectivity

Cu Cat.Cu

Angew. Chem. Int. Ed. 3096 30992008 47 -, , 17 ,

The Challenges of the Silylmetalation ReactionsRv

NAKAMURA, S.; YONEHARA, M.; UCHIYAMA, M.

BN

Si

Chem. Eur. J. 1068 10782008 14 -, , 4 ,

Tris(trimethylsilyl)silane: A Versatile ReagentRv

CHATGILIALOGLU, C.

BN

Si

Chem. Eur. J. 2310 23202008 14 -, , 8 ,

68


Metallosupramolecular Chemistry.Rv

PREFACE FROM LEONARD F. LINDOY.

MJ

Special issue14 articles

Coordin. Chem. Rev. 812 10502008 252 -, , 8, 9,

Bis-Phosphorus Stabilised Carbene ComplexesRv

A perspective article

CANTAT, T.; MÉZAILLES, N.; AUFFRANT, A.; LE FLOCH, P.

MVI

PPR RR R

[M]

PPR RR R

X X

[M]

X = O, NR, S

Dalton Trans 1957 19722008 -, , 15 ,

Light-emitting Iridium Complexes with Tridentate Li gandsRv


WILLIAMS, J. A. G.; WILKINSON, A. J.; WHITTLE, V. L.

MVI

N

N N

N

Ir

N N

N

N N

N

Ir

Dalton Trans 2081 20992008 -, , 16 ,

Cobalt-Rhodium Heterobimetallic Nanoparticle-Catalyzed ReactionsRv


PARK, J. H.; CHUNG, Y. K.

MVI

Co2Rh2

Nanoparticles

Pauson-Khand Reaction Pauson-Khand Type Reaction

SilylcarbocyclizationAminocarbonylation

Hydroformylation

Cyclohydrocarbonylation

Dalton Trans 2369 23782008 -, , 18 ,

69


Suzuki–Miyaura Cross-Coupling ReactionsRv

DOUCET, H.

BJL

A microreview on the development and advances in Pd-catalyzed coupling of aryl, alkenyl or alkyl halides with alkylboronic acids. The remaining challenges in the field are discussed (101 refs).

Pd

Eur. J. Org. Chem. 2013 20302008 -, , 12 ,

Cross-Coupling–Elimination Reactions Mediated or Catalyzed by Zr ComplexesRv

FAÑANÁS, F. J.; RODRÍGUEZ, F.

OC

54 references

Zr

Eur. J. Org. Chem. 1315 13292008 -, , 8 ,

Use of Samarium Diiodide in the Field of Asymmetric Synthesis.Rv

GOPALAIAH, K.; KAGAN, H.B.

CB

Review (65 References)

New J. Chem. 607 6372008 32 -, , 4 ,

Transition Metal-catalyzed Hydrosilylation of Carbonyl Compounds and Imines.Rv

DIEZ-GONZALEZ, S.; NOLAN, S.P.

CB

Review (156 References)

Org. Prep. Proc. Int. 523 5592007 39 -, , 6 ,

70


Arylation, Pd-Catalyzed Aromatic C-H Activation.Rv

LI, B.-J.; YANG, S.-D.; SHI, Z.-J.

MJ

Y

Y = C, N, O .....

Pd catalysis

>54 references

Synlett 949 9572008 -, , 7 ,

Recent Advences in Synthesis of Heterocycles and Cycles via Gold Catalysis.Rv

Heteroatom addition and hydroarylation reactions of alkynes, allenes and alkenes is reported.

SHEN, H. C.

AM

Report (84 references)

Au

Tetrahedron 3885 39032008 64 -, , 18 ,

71

Documents

ddata.over-blog.comddata.over-blog.com/xxxyyy/3/59/81/73/Archives-2008/...Bibliographic Notebooks For Organometallic Chemistry 2008, 26, ( 4) Li N-Metalated Imines as Intermediates