Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Group Migration in AziridinesLi

15 examples.

HODGSON, D.M.; HMPHREYS, P.G.; XU, Z.; WARD, G.

GP

R

N

PG

R

N

H

PGLTMP (3-5 eq.)

THF, -78°C, 90min

PG=CO2tBu, 67-90%PG=PO(OEt)2, 79-95%

Angew. Chem. Int. Ed. 2245 22482007 46 -, , 13 ,

Unusual Reaction of 1-Alkyl-2-(bromomethyl)aziridines with MethyllithiumLi

D’HOOGHE, M.; DE KIMPE, N.

MVI

N

R

BrMe

NH

R

Me

HC CHN

R N

R

Br N

R

N

R2-3 equiv. MeLi

THF or Et2O, 0°C

0° - rt, 18-20h

-

60-75%R = iPr, t-Bu, CHEt2

Chem. Commun. 1275 12772007 -, , 12 ,

Bi-Phenyls and Bi-Naphtyls DerivativesLi

SOLINAS, M.; MEADOWS, R.E.; WILSON, C.; BLAKE, A.J.; WOODWARD, S.

GP

CH3OH

O

SiPh2

1. n-BuLi-TMEDAEt2O, 0°C, 24h

2. Cl2SiPh2

binaphtyl, 55%biphenyl, 60%

Eur. J. Org. Chem. 1613 16232007 -, , 10 ,

αααα-Chloro-ββββ-ethoxyethenyllithium ReagentsLi

ITOH, A.; SAKAI, M.; YOSHIMATSU, M.

CC

(Het)ArH

Cl

OEt

(Het)ArLi

Cl

OEt

(Het)Ar

Cl

OEt

R

OHR'

R"

R'

R

O

(Het)ArnBuLi (1 eq), -78°C

THF, 10 min.

RCOR' (0.67 eq)THF, 10 min.

then H2O

16 Examples Yields = 30 - 98%

Pd

Eur. J. Org. Chem. 2006 20142007 -, , 12 ,

1

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Well-Defined OligothiophenesLi

This process is better than thermal elimination that gives undefined polymers

ZHANG, F.; BAÜERLE, P.

GP

SS

S

Bu Bu

SS

S

Bu Bu

L2PtS

SS

Bu Bu

SS

S

Bu Bu

SS

S

Bu Bu

1. n-BuLi (1 eq.), THF-78°C to 0°C

2. L2PtCl2 (0.5 eq.)THF, -78°C to r.t.

oxidation

chemical or electrochemical

Pt

J. Am. Chem. Soc. 3090 30912007 129 -, , 11 ,

Application of Lithio SilolesLi

WANG, C.; LUO, Q.; SUN, H.; GUO, X.; XI, Z.

GP

LiLi

SiMe3

SiMe3

Ph

Ph

SiMe3

Li

Ph

PhSiMe2

SiMe3

FG

Ph

PhSiMe2

HMPA,

ether, reflux

electrophile

70-90%

7 examples

J. Am. Chem. Soc. 3094 30952007 129 -, , 11 ,

Stereoselective LithiationLi

Calculations support the higher stability of the syn arrangement for the lithio intermediate.

KESSAR, S.V.; SINGH, P.; SINGH, K.N.; VENUGOPALAN, P.; KAUR, A.; BHARAVAM, P.V., SHARMA, A.K.

GP

N

H

BF3

N

H

BF3

H

Li

N

H

BF3

Li

H

N

H

BF3

H

C(OH)Ph2

N

H

BF3

C(OH)Ph2H

+

syn anti

s-BuLi-TMEDA

Et2O, -78°C

Ph2CO

97% 3%

46%

J. Am. Chem. Soc. 4506 45072007 129 -, , 15 ,

Intramolecular Cyclopropanation of Unsaturated Terminal Epoxides and ChlorohydrinsLi

Methodology applied to the synthesis of (+)-β-cuparenoneHODGSON, D. M.; CHUNG, Y. K.; NUZZO, I.; FREIXAS, G.; KULIKIEWICZ, K. K.; CLEATOR, E.; PARIS, J.-M.

MVI

O

OHCl

OLi

NLi

OH

or

J. Am. Chem. Soc. 4456 44622007 129 -, , 14 ,

2

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Homologation of Pinacol Boronates by Enantioenriched Chloroalkyllithium ReagentsLi

Iterative stereospecific reagent-controlled homologation

BLAKEMORE, P. R.; BURGE, M. S.

MVI

O

OB

Bn

ClLi

Bn

O

O

B

Bn

Cl

Bn

Li

O

OB

BnBn

ClLi ClLi

Bn

O

OB

BnBn

Bn

er = 99:1

B

J. Am. Chem. Soc. 3068 30692007 129 -, , 11 ,

Lithiothiophene-2-carboxylatesLi

GANNON, M. K.; DETTY, M. R.

CC

S CO2H

Br

S CO2Li

Li

X

O

Me2N NMe2

XMe2N NMe2

S CO2H

+

-

3- or 5-Br

tBuLi (2.1 eq), THF,

TMEDA (0.25 eq), -78°C

3- or 5-Li

X = O, S, Se

THF, RT then reflux, 12h

(0.25 eq)i)

ii) AcOH (2.1 eq), then HPF6aq

PF6

J. Org. Chem. 2647 26502007 72 -, , 7 ,

Aggregation of Alkyllithiums in THFLi

Computed studies (solvatation number, aggregation state, ...) are reported.

PRATT, L. M.; TRUHLAR, D. G.; CRAMER, C. J.; KASS, S. R.; THOMPSON, J. D.; XIDOS, J. D.

CC

O

OR Li

O

R Li O

O

OLiR

RLiO tetramer

J. Org. Chem. 2962 29662007 72 -, , 8 ,

Pyramidalized AlkeneLi

FORMAN, M. A.; MORAN, C.; HERRES, J. P.; STAIRS, J.; CHOPKO, E.; POZZESSERE, A.; KERRIGAN, M.; KELLY, C.;LOWCHYJ, L.; SALANDRIA, K.; GALLO, A.; LOUTZENHISER, A.

CC

II

LiI

O

Me

Me

OMe Me

Diels AlderCycloaddition 3 Examples

Yields = 13 - 45%for example :

-LiInBuLi (1.2 eq), THF, -78°Cthen 0°C, 2h

ortBuLi (1.7 - 3 eq), -78°C, heptane/Et2O : 20/1then 0°C, 2h

J. Org. Chem. 2996 30052007 72 -, , 8 ,

3

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Enantioselective Synthesis of (-)-Hennoxazole ALi

SMITH, T. E.; KUO, W.-H.; BOCK, V. D.; ROIZEN, J. L.; BALSKUS, E. P.; THEBERGE, A. B.

CC

O

O

N

N

O

TBS

Me

OTBS

MeH

OMe

MeOO

O

N

N

O

OH

MeH

OMe

MeO

Me

MeMe

Br

Me

MeMe

i) LiNEt2, THF, -78°C

ii)

iii) TBAF, THF (-)-Hennoxazole A

Org. Lett. 1153 11552007 9 -, , 6 ,

Lithiation of N-Alkyl-2,3-diphenylaziridinesLi

High diastereoselectivity is reported. Solvent effect is investigated.

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

CC

N

R

Ph

PhN

R

Ph

Ph EN

R

E

Ph Ph

sBuLi, TMEDAhexane or toluene

-78°C, 3 - 4hthen Electrophile

sBuLi, THF,-78°C, 3 - 4h

then Electrophile

R = alkyl 8 examplesYields = 30 - 98%

10 examplesYields = 25 - 98%

Org. Lett. 1263 12662007 9 -, , 7 ,

Vinyl Lithiation of Cis-StilbeneLi

High stereoselectivity is reported.

COTTER, J.; HOGAN, A.-M. L.; O’SHEA, D. F.

CC

Ph

PhPh

Ph

Li

Ph

Li

Ph

Ph

Ph

EsBuLi (2 eq), PMDTA

THF, -25°C, 2h

Electrophile

7 Examples Yields = 32 - 76%

Org. Lett. 1493 14962007 9 -, , 8 ,

Rearrangement of Tritylamines by Phenyl or Aryl MigrationLi

THEODOROU, V.; SKOBRIDIS, K.; KARKATSOULIS, A.

CC

NH2RC6H4

PhPh

Ph2C N C6H4R

C NRC6H4

Ph Ph

.. C NRC6H4

Ph

Ph

..+

NCHPh

Ph

R

Li+

NCH

RC6H4Ph

Li+

nBuLi (1 eq),

THF, -75°C, 1h

R = Me, OMe, Br

- LiH

++

-

. .

-

. .

Tetrahedron 4284 42892007 63 -, , 20 ,

4

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

N-Alkenylations of HeterocyclesLi

C-Alkenylations of N-protected heterocycles using magnesium carbenoïds are reported too.

SAKURADA, J.; SATOH, T.

CC

R

R' Cl

MgCl

R

R'

MgCl

N

N

R

R'

E

N

R

R'

HN Li

N-Lithio heterocycles :

E+ (9 eq), CuI (cat)

-10°C to RT, 1h

7 ExamplesYields = 14 - 71%

10 ExamplesYields = 30 - 71%

-78°C to -10°Ctoluene, Et2O (9 eq)

(3 eq) NH4Cl

Mg

Tetrahedron 3806 38172007 63 -, , 18 ,

Anionic [4+2] CycloadditionLi

MAL, D.; SENAPATI, B. K.; PAHARI, P.

CC

N

O

O

X

P

N

P

R

EO

O

X Li

E

R

N

H

OY

W

Y

W

O

X = H or SO2Ph

LDA (1 eq), -78°C

THF, 30 min. -40°C, THF, 15 min.then RT, 3h

or (1 eq)

or

P = Me, Bn

Tetrahedron 3768 37812007 63 -, , 18 ,

Hauser AnnulationLi

The reaction failed with a more sterically demanding methoxy group instead of fluorine.

PAHARI, P.; SENAPATI, B.; MAL, D.

GP

O

F

O

SO2Ph

O O

FO

O

H

H

OHO

O

+t-BuOLi, THF

-60°C 84%

Tetrahedron Lett. 2635 26382007 48 -, , 14 ,

Access to 2-Fluoroalkyl IndolesMg

GE, F.; WANG, Z.; WAN, W.; HAO, J.

OS

N

Br

Me

CF3

ClN

Me

CF3

H

Mg, THF

0 °C - r.t., 2 h.82%

These nucleophilic substitutions have been demonstrated as the most efficient way to access new generation of interesting fluorine-containing indole derivatives.

Synlett 447 4502007 -, , 3 ,

5

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

One-Pot Double C-AcylationMg

Double intermolecular C-acylation give the corresponding dicarbonyl compounds in good yields.

MATSUNAMI, M.; SAKAI, N.; MORIMOTO, T.; MAEKAWA, H.; NISHIGUCHI, I.

OS

O

Et Cl

OEt

Et O

+ 78%Mg

DMF

Synlett 769 7742007 -, , 5 ,

Cationic Alkyl Rare-Earth Metals Complexes for Dienes Living (Co)Polymerization.Sc

In-situ generated cations display outstanding performances in diene living polymerization and block copolymerization.

ZHANG, L.; SUZUKI, T.; LUO, Y.; NISHIURA, M.; HOU, Z.

GR

N

LnPPh2Ph2P

(THF)nMe3Si SiMe3

[HNMe2Ph][B(C6F5)4]

THF

N

LnPPh2Ph2P

THFTHF

Me3Si

[B(C6F5)4]

Ln= Sc (n=0), Y and Lu (n=1)

YLu

Angew. Chem. Int. Ed. 1909 19132007 46 -, , 11 ,

Arene Complexes of Organoscandium Cations.Sc

Arene displacement kinetic studies and reactivity towards diphenylacetylene are presented.

HAYES, P. G.; PIERS, W. E.; PARVEZ, M.

GR

N

NSc

Ar

Ar

Me

Me

[CPh3][B(C6F5)4]

Ar= 2,4,6-Me3C6H2

Rn

N

NSc

Ar

Ar

Me

Rn

[B(C6F5)4]

Chem. Eur. J. 2632 26402007 13 -, , 9 ,

Transesterification of Carboxylic EstersSc

A broad range of different functional groups was tolerated.

LE REMME, N.; KOSCHEK, K.; SCHNEIDER, C.

OS

O

OEt

O

OMe

Sc(OTf)391%

(1 mol%)

MeOH, 64 °C, 10 h

Synlett 491 4932007 -, , 3 ,

6

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Catalytic Diastereoselective AllylationY

DUEÑES, R.A.; MORKEN, J. P.

OS

O OBu

Me

Bu

SiMe3

O

Me

BuCH2Cl2, 22 °C.+

Y(OTf)3 or Sc(OTf)3(0.2 equiv.)

60%

d.r. (>20:1)

The allylation of Oshima–Utimoto products is an efficient process and, with appropriate substituents can provide highly functionalized and stereoselectived furans.

Sc

Synlett 587 5902007 -, , 4 ,

Rare-Earth Metals Tetraaluminate Derivatives.La

This study underlines the different alkylating power of rare-earth and aluminium methyl functions.

ZIMMERMANN, M.; TÖRNROOS, K. W.; ANWANDER, R.

GR

N

N NAr Ar

N

N NAr ArLa

Me MeMeMe

Al AlMe

MeMeMe

THF

-AlMe3(THF)N

N NAr ArLa

Me

Me

AlMe Me

O

THF

-THFN

N NAr ArLa

Me MeAl

MeMe

Ar=2,6-iPrC6H3

La(AlMe4)3

NdYAl

Angew. Chem. Int. Ed. 3126 31302007 46 -, , 17 ,

Catalytic Asymmetric Michael Malonate Addition to α,βα,βα,βα,β-Unsaturated N-Acylpyrroles.La

Ligand tuning affords good yields and enantioselectivity.

PARK, S.-Y.; MORIMOTO, H.; MATSUNAGA, S.; SHIBASAKI, M.

GR

O

RN

X

+Z

Z La(OiPr)3 (10%)

Ligand (10%)

O

N

X R

Z

Z

N

O

X = Z = CO2Bn 76-87% yield78-96% ee

7 examples

Ph

OH

O

HO

HOLigand:

Tetrahedron Lett. 2815 28182007 48 -, , 16 ,

SmI2-Mediated Saccharide CouplingSm

Synthesis of neuraminic acid disaccharide, precursor of oligosialic acids and gangliosides.

YUAN, X.; RESS, D. K.; LINDHARDT, R. J.

AS

OAc

OAcOAc

AcNHOAc

SO2Ph

CO2Me

OAll

OAll

Ac2N

OAll

SPh

CO2All

O

OAll

OAll

Ac2N

OAll

SPh

CO2All

OAc

OAcOAc

AcNHOAc

CO2Me

OH+

SmI2 (5 equiv.)

THF

35%, R/S 1/1

J. Org. Chem. 3085 30882007 72 -, , 8 ,

7

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Reactivity of Cyclopropanic δδδδ-Oxo-αααα,ββββ-Unsaturated Esters towards SmI2.Sm

Mechanistic pathways are discussed to account for the selectivity of the reaction.

CAMMOUN, C.; ZRIBA, R.; BEZZENINE-LAFOLLÉE, S.; GUIBÉ, F.

GR

O

CO2Me

PhPh

2.2 SmI2

4 tBuOH

PhPh

O

O

Tetrahedron 3728 37362007 63 -, , 18 ,

Samarium-Induced Reductive Cyclization in Natural Product Synthesis.Sm

Short synthesis of a lactone found in Greek tobacco is described.

CLARK, J. S.; HAYES, S.T.; BLAKE, A. J.; GOBBI, L.

GR

SmI2

MeOHOH

O

EtO2C OH

HO

EtO2C

HO

HH

OO

CH3

Tetrahedron Lett. 2501 25032007 48 -, , 14 ,

[3+2] Cycloaddition of N-Arylimines and EpoxidesYb

Novel synthetic method for the construction of five-membered heterocycles.

YU, C.; DAI, X.; SU, W.

OS

OCl N

H

ON

Cl

Yb(OTf)3 (10 mol%)

CH2Cl2, reflux+ 85%

Synlett 646 6482007 -, , 4 ,

Cycloaddition of AllenyltrimethylsilylthioketenesYb

Yb(OTf)3-catalyzed [4+2] cycloaddition of allenyltrimethylsilylthioketenes with arylaldimines

AOYAGI, S.; OHATA, S.; SHIMADA, K.; TAKIKAWA, Y.

OS

SMe3Si

Me NPh

N

S

Me3Si

Me PhBn

BnYb(OTf)3 (20 mol%)

CHCl3, reflux, 12 h.

+

(0.67 equiv.)

65%

Synlett 615 6182007 -, , 3 ,

8

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Total Synthesis of DiscodermolideTi

Other key step: Kocienski rearrangement (Cu)

DE LEMUS, E.; PORÉE, F.-H.; COMMERÇON, A.; BETZER, J.-F.; PANCRAZI, A.; ARDISSON, J.

BC

OO

OH

HO

OH O

OH

8

14

O SnBu3

OH

8

14

O

(iPr)2N

SnBu3

O

HO O

(iPr)2N

Discodermolide

Ti(OiPr)3

+

pentane/cyclohexane-78°C, 3h, 84%

SnCu

Angew. Chem. Int. Ed. 1917 19212007 46 -, , 11 ,

Metal Mediated Reactivity of Alkenynyl Carbamate: Ti vs LiTi

BOU CHEDID, R.; BRÜMMER, M.; WIBBELING, B.; FRÖHLICH, R.; HOPPE, D.

BC

OCb

PhOCb=

O

O

N(iPr)2

S= Sparteine

Ph

S.LiO

O

N(iPr)2

Ph

S.LiO

O

N(iPr)2

OCb

.

Ph OH

OCb

.

Ph OH

Ph

(OiPr)3Ti OCb

Ph

(OiPr)3Ti OCb

OCb

Ph

HO

OCb

Ph

HO

nBuLiS

1-

2-H2O

O

1-

2-H2O

O

crystallization15h, -78°C

81%ee 94%

61%ee 94%

1-

2-H2O

O

1-

2-H2O

O

ClTi(OiPr)3

inversion

ClTi(OiPr)3

inversion

Li

Angew. Chem. Int. Ed. 3131 31342007 46 -, , 17 ,

Regiodivergent Epoxide OpeningTi

Other examples

GANSAUER, A.; FAN, C.-A.; KELLER, F.; KEIL, J.

BPH

O

R'R

[Ti] 0.1 equiv

Mn, Coll•HCl1,4-C6H8

R'R

OH

R'R+

HO

[Ti] = )2TiCl2R = n-Pr, R' = (CH2)2CO2t-Bu

ee 80%

13% (ee 8%) 71% (ee 99%)

using ent-[Ti] 76% (ee 94%) 10% (ee 50%)

Mn

J. Am. Chem. Soc. 3484 34852007 129 -, , 12,

Coupling of Benzylic HalidesTi

BARRERO, A. F.; HERRADOR, M. M.; QUILEZ DEL MORAL, J. F.; ARTEAGA, P.; AKSSIRA, M.; EL HANBALI, F.;ARTEAGA, J. F.; DIEGUEZ, H. R.; SANCHEZ, E. M.

BPH

Y

XCp2TiCl (0.2 equiv)

Mn (8 equiv)THF, rt

R R

R

or R

R

(X = hal, Y = H) (X, Y = hal)

Mn

J. Org. Chem. 2251 22542007 72 -, , 6 ,

9

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Activation of Bis(pyrrolylaldiminato) Titanium Poly merization Catalysts with MAOTi

1H and 13C NMR investigation of the mechanism

BRYLIAKOV, K.P.; KRAVTSOV, E.A.; BROOMFIELD, L.; TALSI, E.P.; BOCHMANN, M.

AN

N

N

NPhTi

NPh

Cl

Cl

I

MAO*

Al:Ti = 10

N

N

NPhTi

NPh

Cl

13CH3

I2

MAO*

Al:Ti = 50

N

N

NPhTi

NPh

Cl

13CH3

+

MeMAO*_

C2H4 PE

MAO* = MAO-13CI3

Organometallics 288 2932007 26 -, , 2 ,

Synthesis and Structure of Titanatranes Containing Tetradentate Trianionic Donor LigandsTi

the complexes were tested in the ethylene polymerization reaction

PADMANABHAN, S.; KATAO, S.; NOMURA, K.

AN

Ti(OR')4 + [(HO-2,4-tBu2C6H2-6-CH2)2(HOCH2CH2)N]

N

O Ti O

OOR'

R

R

R

R

CH2Cl2 or tol

-30 to 25°C6h

R,R' = tBu,iPrR,R' = tBu,tBu

Organometallics 1616 16262007 26 -, , 7 ,

Biaryl Amidate Complexes in Catalytic Hydroamination/Cyclization of AminoalkenesTi

Hydroamination/cyclization of aminoalkenes: Structure-activity relantioships for group 4 complexes

GOTT, A.L.; CLARKE, A.J.; CLARKSON, G.J.; SCOTT, P.

AN

NH2H2N

2 RCOClEt3N

CH2Cl2

NHH

N

R

OO

R

TiBn4Me

Me

N

N O

R

O

R

TiBn

BnR = Me, Et, tBu, Mes

Zr

Organometallics 1729 17372007 26 -, , 7 ,

Primary tert-Alkylamines from NitrilesTi

TOMASHENKO, O.; SOKOLOV, V.; TOMASHEVSKIY, A.; DE MEIJERE, A.

BJL

R1CN

R2MgXTi(Oi-Pr)4R3MgX

NH2R2R1

R3

25-72%

Synlett 652 6542007 -, , 4 ,

10

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Synthesis of Tetraarylethenes via Cross McMurry CouplingTi

14 examples, yields: 59-80%.

DUAN, X.F.; ZENG, J.; LU, J.W.; ZHANG, Z.B.

GJ

C6H

4-pOH

Ph

Ph

PhO

Ph

PhO

p-HOC6H

4

Ph TiCl4-Zn-Pyr

+ 66%

(1.2 equiv)

(5 equiv)

THF, 25 h, reflux

Zn

Synthesis 713 7182007 -, , 5 ,

Catalytic Enantioselective Addition of Dimethylzinc to KetoneTi

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

TJ

Ph

O

Cl

Ti(OiPr)4

PhMe, 25 °CHOCSAC 5 mol%

+ Me2Zn PhCl

Me OH

HNNHO2S SO2

OHHO HOCSAC90%; ee 80%

Zn

Tetrahedron Asymm. 400 4052007 18 -, , 3 ,

Synthesis of αααα-Methylene-γγγγ-butyrolactonesTi

PAIRA, M.; BANERJEE, B.; JANA, S.; MANDAL, S.K.; ROY, S.C.

TJ

R

CHO

R

OO

CO2MeBr+

1. Cp2TiCl/THFrt, 5 h

2. 20% H2SO45-11 h

13 examples48-68%

Tetrahedron Lett. 3205 32072007 48 -, , 18 ,

Stereoselective Zr-mediated Ring ContractionZr

3 new C-C bonds and 3 new stereogenic centers are formed during this process

BARLUENGA, J.; AVAREZ-RODRIGO, L.; RODRIGUEZ, F.; FANANAS, F.J.; SORDO, T.L.; CAMPOMANES, P.

BC

Cp2ZrCl2

THF, -78°C1-

2-

-78°C to 25°C3- electrophile4- H+

OAr

MR

M= Li, MgBrR

OHAr

HE

R

E OH

Ar

0-56%

+

15-86%single diastereomer

14 examples

MgLi

Angew. Chem. Int. Ed. 2607 26092007 46 -, , 15 ,

11

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Reduction of Amides to Aldehydes. Scope and Mechanism.Zr

Many functional groups tolerated (esters, nitriles, nitro ...)

SPETSTOSER, J. T.; WHITE, J. M.; TUNOORI, A. R.; GEORG, G. I.

BPH

R N

OR'

R"

Cp2ZrHCl (1.2 equiv)

THF, 30 minR H

O

up to 99%

J. Am. Chem. Soc. 3408 34192007 129 -, , 11 ,

Gas-Phase Reactions of Bis(h5-Cp)methylzirconium Cations with Ketones and AldehydesZr

reactions in gas phase studied by Fourier transform ion cyclotron resonance mass spectrometry

AKSENOV, A.A.; CONTRERAS, C.S.; RICHARDSON, D.E.; EYLER, J.R.

AN

Cp2Zr CH3+

+ OCD3

CD3Cp2Zr

CH3+

OCD3

CD3

Cp2Zr

OCD3

CD3

H3C+

Cp2ZrCD3

+

OCH3

CD3

Organometallics 478 4882007 26 -, , 3 ,

1-Zircona-2-cyclohexenes: Novel Synthesis and Preliminary ReactionsZr

WANG, Q.; FAN, H.; XI, Z.

AN

I

R2R1 Cp2ZrHClTHF, r.t., 1h Cp2Zr

ICl 2eq. t-BuLi-78°C, 1h

Cp2Zr

R1 R2 H+ (or D+)-78°C

CH2

(D) H

R2R1

(D) H

Organometallics 775 7772007 26 -, , 4 ,

Generation of Heteroaromatic ZirconoceneZr

IKEUCHI, Y.; SAITOH, T.; TAGUCHI, T.; HANZAWA, Y.

TJ

XOR

TMS1. "Cp2Zr"

2. Cu(I) cat.

BrX

TMS

R

R9 examples

37-85%

Cu

Tetrahedron Lett. 2477 24802007 48 -, , 14 ,

12

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

N-C Bond Formation from CO2 and an Hf-based ComplexHf

BERNSKOETTER, W.H.; LOBKOVSKY, E.; CHIRIK, P.J.

BC

HfN

HfN

*Cp

*Cp

Cp*

Cp*

NN

OHfHf

O

O O

*CpCp* Cp*

Cp*

HfII

*Cp

*Cp

NN

OTMSTMSTMS

TMSO

O O

+TMSI

excess

2 CO2

Angew. Chem. Int. Ed. 2858 28612007 46 -, , 16 ,

Complexation of Bis(trimethylsilyl)acetylene by DecamethylhafnoceneHf

the first complexes of well-defined hafnium alkyne complexes with an intact alkyne

BEWERIES, T.; BURLAKOV, V.V.; BACH, M.A.; ARNDT, P.; BAUMANN, W.; SPANNENBERG, A.; ROSENTHAL, U.

AN

Cp*2HfCl2

LiMe3SiC2SiMe3

(tol.)

- 2 LiClCp*2Hf

SiMe3

SiMe3

Organometallics 247 2492007 26 -, , 2 ,

Hf Bis(phenoxyimino)dibenzyl Complexes. Their Activation toward Olefin PolymerizationHf

AXENOV, K.V.; KLINGA, M.; LEHTONEN, O.; KOSKELA, H.T.; LESKELA, M.; REPO, T.

AN

R1

R2

OH NR3

R1O

R2

Hf

NR3

Cl

Cl

2

1) BuLi or NaH in Et2O

2) HfCl4 in PhCH3

R1 = t-Bu, R2 = H, R3 = CH2PhR1 = R2 = cumyl, R3 = CH2PhR1 = t-Bu, R2 = H, R3 = C6F5R1 = R2 = cumyl, R3 = C6F5

Organometallics 1444 14602007 26 -, , 6 ,

Tantalum Phosphoniomethylidyne Complexes.Ta

Formation mechanism is proposed.

LI, X.; WANG, A.; WANG, L.; SUN, H.; HARMS, K.; SUNDERMEYER, J.

GR

TaCl Cl

ClCl

H2C PPh35Ta

C CCl

Ph3P

HPPh3

H2C PPh32Ta

CC

CPh3P

H

PPh3

HPPh3

-3 [Ph3PCH3]Cl - [Ph3PCH3]Cl

Organometallics 1411 14132007 26 -, , 6 ,

13

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Water-Soluble Organometallic Tantalum Derivatives.Ta

First examples of water-soluble organometallic tantalum species.

CONDE, A.; FANDOS, R.; OTERO, A.; RODRÍGUEZ, A.

GR

TaH3C

NO

O OTf

xs H2O

RT, 12 hrs TaH3C

NO

OOTfOH2

xs H2O

90°C, 30 min. TaHO

NO

OOTfOH2

Organometallics 1568 15702007 26 -, , 7 ,

Catalytic Enantioselective Methallylation of Aldehydes Cr

HARGADEN C.G.; MCMANUS H.A.; COZZI P.G.; GUIRY P.J.

AE

R H

O

BrR

OH

+

(i) CrCl3 (0.1 eq.), Mn (3 eq.)ligand (0.12 eq.), DIPEA (0.3 eq.)Me3SiCl, THF/CH3CN (7:1), 16h, RT

(ii) 1M HCl, THF*

yield : 41 to 92%ee : 33 - 95%R = Ph, p-MeO-Ph, p-Cl-Ph, C5H10, C6H13, Ph(CH2)2

NH

O

NBn

N

O

t-Bu

Ligand :

Mn

Org. Biomol. Chem. 763 7662007 5 -, , 5 ,

Epoxidation in Ionic Liquid.W

8 examples. Slight decrease of efficiency with the reycling.

KUMAR, A.

MJ

R2

R1

R3

[bmim]4[W10O23] (0.0036 eq.)

[bmim][BF4], 55 °C, 1.5-3 h

Conversion: 48-97%Selectivity: 74-95%

R2

R1

R3O

Catal. Commun. 913 9162007 8 -, , 6 ,

Oxidation of Alcohols Catalyzed by Mn-PorphyrinsMn

REZAEIFARD, A.; JAFARPOUR, M.; KARDAN MOGHADDAM, G.; AMINI, F.

PL

R1 R2

OH

R1 R2

OBu4NHSO5/CH3CN

Mn(TPP)OAc/Prrt

R1 = Aryl, allyl, alkylR2 = H, aryl, alkyl

80-98% yield

Bioorg. Med. Chem. 3097 31012007 15 -, , 8 ,

14

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Triaquatricarbonyl Cation and Its Conjugate BaseRe

Only with PF6-, both the cation and its conjugated base co-crystallized.

HERRICK, R. S.; ZIEGLER, C. J.; ÇETIN, A.; FRANKLIN, B. R.

HJR

Re COH2O

H2OOH2

OC CO

Re COH2O

H2OOH

OC CO

P

F

F

F F

FF

Eur. J. Inorg. Chem. 1632 16342007 -, , 12 ,

Hydrido Complexes with Polypyridine and Phosphonite LigandsRe

Extension to tolyl- and t-Butylacetylene, 69 and 73%, respectively.

ALBERTIN, G.; ANTONIUTTI, S.; CASTRO, J.; GARCIA-FONTAN, S.; SCHIPILLITI, G.

HJR

P = PPh(OEt)2

Green solid, 68%

+

[ReH2(bpy)P3]+ + xs HCCPh

ClCH2CH2Cl,reflux, 1 h

Re

N

N

P

P

PC

C

CC

H

H

HH

Ph

Ph

Eur. J. Inorg. Chem. 1713 17222007 -, , 12 ,

Mechanistic Insight into Hydrosilylation Reactions Catalyzed by Re ComplexesRe

The silane does not add across the metal-ligand multiple bond

DU, G.; FANWICK, P. E.; ABU-OMAR, M. M.

MVI

Re

O

ClPh3P Cl

ClH

SiEt3O

H

Ph

OPhSiEt3

H H

δ-

δ+

Si

J. Am. Chem. Soc. 5180 51872007 129 -, , 16 ,

A New Chiral Diiron Catalyst for Enantioselective EpoxidationFe

MARCHI-DELAPIERRE, C.; JORGE-ROBIN, A.; THIBON, A.; MÉNAGE, S.

LF

O

OCH3CO3HCH3CN / 0 °C / 2 min

O

OO

63%

FeO

Fe

N N

N N

N N

N N

*

*

*

*

X X

NN

*=

N NH H

bisPB

Chem. Commun. 1166 11682007 -, , 11 ,

15

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Acylnitroso Dienophile Generation Mediated by Metal Catalysis ProcessFe

46 exemples/conditions are described.

ADAMO, M. F. A.; BRUSHI, S.

DL

BocNHOH+ Diene Product

Mt (5mol%), Ligand (15 mol%)

H2O2, DCM or THF, rt20 to 11520 min

27-95% yield

Ligand: HOCH2CH2NH2, H2NCH2CH2NH2, Et3N

Mt: Fe(III), Cu(II), Cu(I), Ni(II), Ru(III)

Cu,Ru,Ni

J. Org. Chem. 2666 26692007 72 -, , 7 ,

Iron Carbonyl Mediated Spirocyclization Reactions: Dynamic DiastereoselectivityFe

PEARSON, A. J.; SUN, H.; WANG, X.

DL

PMBN

O

Bn

EtO2CFe(CO)3

+NPMB

O

Bn

CO2Et(OC)3Fe Benzene, CO,

350nm, 85°C,

72%PMBN

O

BnH

CO2Et Fe(CO)3

PMBNO

BnH

CO2Et Fe(CO)3

+

J. Org. Chem. 2547 25572007 72 -, , 7 ,

Iron-Catalyzed Arylmagnesiation of Aryl(alkyl)acetylenes Fe

YAMAGAMI, T.; SHINTANI, R.; SHIRAKAWA, E.; HAYASHI, T.

CS

Ar2MgBr

+

Ar1R

Fe(acac)3 (5 mol%)IPr( 20 mol%)

THF, 60°C, 16h

MgBrAr2

R Ar1

IPr14 examples, up to 91% yield

up to 95:5 E/Z

N N

Mg

Org. Lett. 1045 10482007 9 -, , 6 ,

Diastereoselective Ortho-Lithiation of Acetyl FerroceneFe

FERBER, B.; TOP, S.; HERSON, P.; JAOUEN, G.

BC

Fe Me

NMeO

tBu Fe Me

NMeO

tBu

I

Fe Me

OI

dr>95/5 73%(2 steps)

HClaq / THF

silica gel

1- tBuLi

2- THF

I

I

Li

Organometallics 1686 16912007 26 -, , 7 ,

16

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Synthesis of Nitrogen-Substituted FerrocenesFe

12 examples, yields: 31-84%.

OZCUBUKCU, S.; SCHMITT, E.; LEIFERT, A.. BOLM, C.

GJ

Fe

I

NH

Fe

N

+62%

CuI (1 equiv)

DMSO, 90°C, 18 h(2 equiv)

Cu

Synthesis 389 3922007 -, , 3 ,

Coupling of Cyclopropylcarbene–Chromium Complex with Ferrocenyl AlkynesFe

ZORA, M.; TUMAY, T. A.; BUYUKGUNGOR, O.

PL

OCH3

Cr(CO)5

Fe

R

1% aq. dioxane

100°C, 6h

O

OCH3

HO

Fc

HR

O

O

Fc

R

Fc = Ferrocene

R = CH3, 36% for 1, 17% for 2R = Bn, 16% for 1, 57% for 2R = Ph, 31% for 1, 55 for 2R = Fc, 18 for 1, 32 for 2

1 2

++

Cr

Tetrahedron 4018 40262007 63 -, , 19 ,

Biferrocene Diphosphine Ligand with only Planar ChiralityFe

The diphosphine ligand was used in Rh(I)-catalyzed asymmetric hydrogenation of β-keto sulfones.ZHANG, H.-L.; HOU, X.-L.; DAI, L.-X.; LUO, Z.-B.

PL

FePh2PFe

PPh2 OH

Fe

S

PPh2 OH3B

Fe

CHO

PPh2H3B

(R,R)

1) t-BuLi, THF, -78°C

2) + (R)-13) DABCO, toluene 60°C

(R)-1 89%

+

Rh

Tetrahedron Asymm. 224 2282007 18 -, , 2 ,

Planar Chiral Iridium Ferrocenyloxazolinylphosphine ComplexesFe

These complexes were applied as catalysts in the enantioselective hydrogenation of olefins.

LI, X.; LI, Q.; WU, X.; GAO, Y.; XU, D.; KONG, L.

PL

Fe

PPh2

N

O

R

Fe

PPh2

N

O R

Ir

+

X-1) [Ir(cod)Cl]2; 2) NaBArFor 1) [Ir(cod)Cl]2; 2) NaPF6

or 1) [Ir(cod)Cl]2

R = Me, i-Pr, t-Bu, PhX = BArF, PF6, Cl

Ir

Tetrahedron Asymm. 629 6342007 18 -, , 5 ,

17

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Ferrocenyl Substituted AziridinylmethanolsFe

The synthesized diastereomers has been used as ligands in enantioselective conjugate addition of diethylzinc to enones.

ISLEYEN, A.; DOGAN, O.

PL

Fe

O1) Br2

2)

NH2

Me PhH Fe

ON

H

Me PhH

S

S

S

S 54% + R 42%

Fe

OHN

H

Me PhH

S

SR

89% yield>99% de

L-selectrideTHF, -78°C

ZnNi

Tetrahedron Asymm. 679 6842007 18 -, , 5 ,

Cationic Iron-Catalyzed Intramolecular Hydroalkoxyl ation of OlefinsFe

KOMEYAMA, K.; MORIMOTO, T.; NAKAYAMA, Y.; TAKAKI, K.

PL

Ph

Ph

OHO

Ph

Ph

R1

R1 = H, CH3

R1

94-97%

hydroxyolefin (0.5 mmol)FeCl3 (10 mol%)

AgOTf (30 mol%), DCE (5 mL)80°C

Tetrahedron Lett. 3259 32612007 48 -, , 18 ,

Synthesis of Multifunctionalized 1,2,4-Triazolidines via Three Component CouplingRu

R1, R2: aryl; catalyst: ruthenium porphyrin.

WANG, M.-Z.; HAI-WEI XU, H.-W.; LIU, Y.; WONG, M.-K.; CHE, C.-H.

AF

R1 NR2 N N

EtOOC

Cl

N2

OR*

O [Ru(2,6-Cl2TPP)(CO)](1 mol %)

ClCH2CH2Cl45 °C, 12 h

10 - 64 %, 21 - 84 % de

EtOOC COOEt

R2R1

OR*

O

* *+ +

Ph

R*=

Adv. Synth. Catal. 2391 23962006 348 -, , 16-1

,

Repetitive Application of a Fluorous Chiral BINAP–Ru ComplexRu

A trisperfluoroalkylsilyl-modified (S)-BINAP ligand has been prepared.

HORN, J.; BANNWARTH, W.

LF

R1

R2

O

O Ru-RF-BINAPFSG

10-30 bar H260 °C

R1

R2

O

O

H

*

RF-BINAP:(RF)3Si

(RF)3Si

PPh2PPh2

RF = CH2CH2C8F17

Eur. J. Org. Chem. 2058 20632007 -, , 13 ,

18

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

RuCl2(dmso)4 Catalyzes the Solvent-Free Indirect Friedländer Synthesis of QuinolinesRu

MARTINEZ, R.; RAMÓN, D. J.; YUS, M.

LF

NH2

X

R2

R1

R3

XR4

RuCl2(dmso)4

KOtBuPh2CO, solvent-free,100 °C

N

R2

R1R3

43-99%

Eur. J. Org. Chem. 1599 16052007 -, , 10 ,

Olefin Methathesis on ComplexesRu

X-Ray structure is given for each new product.

CHEN, W.-Z.; PROTASIEWICZ, J.D.; DAVIS, S.A.; UPDEGRAFF, J.B.; MA, L.-Q.; FANWICK, P.E.; REN, T.

GP

NAr

N

Ru

Ar

N Ru

Ar

ArCl

O

O

N

Ar

N

Ar

n

n

NAr

N

Ru

Ar

N Ru

Ar

ArCl

O

O

N

Ar

N

Ar

n

n

(Cy3P)2Cl2Ru(=CHPh) (5%)

CH2Cl2, reflux, overnight

Inorg. Chem. 3775 37822007 46 -, , 9 ,

Tandem Catalytic Carbene Addition/Bicyclization of EnynesRu

MONNIER, F.; VOVARD-LE BRAY, C.; CASTILLO, D.; AUBERT, V.; DÉRIEN, S.; DIXNEUF, P. H.; TOUPET, L.; IENCO,A.; MEALLI, C.

MF

XX R

Y

RRu

Cl

N2CHY[Ru] 5%

[Ru] =

J. Am. Chem. Soc. 6037 60492007 129 -, , 18 ,

Synthesis of Bridged PaclitaxelsRu

9 exemples, yields: 60-87%; study of paclitaxel-tubulin interactions.

GANESH, T.; YANG, C.; NORRIS, A.; GLASS, T.; BANE, S.; RAVINDRA, R.; BANERJEE, A.; METAFERIA, B.; THOMAS,S.L.; GIANNAKAKOU, P.; ALCARAZ, A.A.; LAKDAWALA, A.S. ; SNYDER, J.P.; KINGSTON, D.G.I.

GJ

O

R1O

O

O

O

XO

ONH

O OH

AcO OSiEt3

Ph

OBz

H

O

R1O

O

O

O

OO

NH

O OH

AcO OSiEt3

Ph

OBz

H

O

(H2IMes)(PCy

3)(Cl)

2Ru=CHPh

65%

CH2Cl2, rt, 4 h

J. Med. Chem. 713 7252007 50 -, , 4 ,

19

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Stereoselective Approach to Duprezianane, Polyquinane and Sterpunane FrameworkRu

SINGH, V.; PRAVEENA, G. D.; KARKI, K.; MOBIN, S. M.

DL

R1O

R

O

H

endo/exo mixtureDCM, rt, Grubb's I catalyst (4 mol%)R

1OO

R2 R2R: Me, R1: Me, R2: H 55%

R: H, R1: Me, R2: H 35%

R: Me, R1: H, R2: Me 49%

yield

J. Org. Chem. 2058 20672007 72 -, , 6 ,

Attenol A: Reductive Cyclyzation ApproachRu

LA CRUZ, T. E.; RYCHNOVSKY, S. D.

DL

OO OO

OO OO

2) H2, 100psi

93%

1) Grubb's II catalyst

cat.

RuPCy3

PhCl

ClNN MesMes

Cu,In,Rh

J. Org. Chem. 2602 26112007 72 -, , 7 ,

Enantioselective Synthesis of Gypsy Moth Pheromone DisparlureRu

PRASAD, K. R.; ANBARASAN, P.

DL

C10H21

OTs

OBn+

1) Grubb's II catalyst(5 mol%)

DCM, reflux, 6h, 92%

C10H21

OTs

OBn

2) H2, Pd/C, MeOH, rt, 3h, 90%

J. Org. Chem. 3155 31572007 72 -, , 8 ,

Total Synthesis and Bioactivity of an Unnatural Enantiomer of Merrilactone ARu

INOUE, M.; LEE, N.; KASUYA, S.; SATO, T.; HIRAMA, M.; MORIYAMA, M.; FUKUYAMA, Y.

DL

OH

HO

ODCBODCB

OH

HO

ODCBODCB

Grubb's I catalyst(0.1 equiv.)

DCM, reflux, 5h

ODCBODCB

OH

OH

Pb(OAc)4

85%

ODCBODCB

O

O

DCB: dichlorobenzyl

J. Org. Chem. 3065 30752007 72 -, , 8 ,

20

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

A Rapid and Simple Cleanup Procedure for Metathesis ReactionsRu

GALAN, B. R.; KALBARCZYK, K. P.; SZCZEPANKIEWICZ, S.; KEISTER, J. B.; DIVER, S. T.

CS

N N

RuPCy3

Cl

Cl

Ph

metathesis-active

MeOH, rt, 30 min

CNCH2CO2K N N

RuPCy3

ClC N CH2CO2KCNH2CKO2C

metathesis-inactive, easy to remove

Ph

Cl

Org. Lett. 1203 12062007 9 -, , 7 ,

Ru(II), Rh(III), Ir(III) for the Cyclometalation of Primary Benzyl AminesRu

SORTAIS, J.-B.; PANNETIER, N.; HOLUIGUE, A.; BARLOY, L.; SIRLIN, C.; PFEFFER, M.; KYRITSAKAS, N.

PG

RuCl

Cl

2 CAr-H

NH2

+ RuCAr

NH2NCCH3

PF6

NaOH, KPF6

CH3CN, rt, 72h

RhIr

Organometallics 1856 18672007 26 -, , 8 ,

Ru(II) for the Cyclometalation of Secondary Benzyl AminesRu

SORTAIS, J.-B.; PANNETIER, N.; CLÉMENT, N.; BARLOY, L.; SIRLIN, C.; PFEFFER, M.; KYRITSAKAS, N.

PG

RuCl

Cl

2 CAr-H

NHR

+ RuCAr

NHRNCCH3

PF6

NaOH, KPF6

CH3CN, rt, 72h

Organometallics 1868 18742007 26 -, , 8 ,

Base Free Synthesis of N-Heterocyclic Carbene Metal Complexes Ru

BLUM, A. P.; RITTER, T.; GRUBBS, R. H.

PG

N

N

C6F5

H

R

R

+ [M]PhCH3, 70°C N

N[M]

R

R

+ C6F5H

IrRh

Organometallics 2122 21242007 26 -, , 8 ,

21

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Spiro-Bridged bis(αααα-Amino Acid) Derivative Based on RCM ReactionsRu

ANDREI, M.; EFSKIND, J.; UNDHEIM, K.

PL

MeO2C

CO2Me

NHAc

AcHN

MeO2C

AcHN

NHAc

CO2Me

isomer ratio 3:2

NHAc

MeO2C

NHAc

CO2Me

Grubbs-II cat. (10%)

toluene, 85°C, 4h

73%

+

Tetrahedron 4347 43552007 63 -, , 20 ,

Synthesis of Cholaphanes by RCMRu

CZAJKOWSKA, D.; MORZYCKI, J. W.

PL

OH

O

O

O

O

OH

O

OH

OOH

OH

O

O

O

O

OHO

OH

O

OH

Grubbs I(25 mol%)

72%

E/Z = 8:1

Tetrahedron Lett. 2851 28552007 48 -, , 16 ,

Pd-Catalyzed Arylation/RCM Approach to AzabicyclesRu

MARTYNEZ-ESTYBALEZ, U.; SOTOMAYOR, N.; LETE, E.

PL

I

NH2

R1

NH2

R1 = CH2CH=CH2, CH=CHCH3, CH=CH2

R1SnBu3/[Pd]

PPh3

32-80%

R1

NMe

R2

Ph NMe Ph

( )n

n = 0,1,2

Grubbs' I or IIcatalysts

CH2Cl2, reflux

8-75%

1) PhCHO2) R2MgCl

3) LDA, MeI

R2 = CH2CH=CH2, CH=CH2

PdSnMg

Tetrahedron Lett. 2919 29222007 48 -, , 16 ,

Osmium(II) and Ruthenium(II) Arene Maltolato ComplexesOs

Rapid Hydrolysis and Nucleobase Binding (X-Ray, dynamic NMR studies, DFT calculations)

A.F.A. PEACOCK, M. MELCHART, R.J. DEETH, A. HABTEMARIAM, S. PARSONS, P.J. SADLER

CM

Os

O

OX

O

n+

X = Cl, n = 0X = OH2, n = 1X = OH, n = 0X = nucleobase, n = 1

Ru

Chem. Eur. J. 2601 26132007 13 -, , 9 ,

22

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

A Ditertiary-Phosphane-Bridged Heteronuclear ClusterOs

Synthesis and Reactivity with Alkynes

Y.L.K. TAN, W.K. LEONG

CM

Ru3(CO)12 + 3 C2H4

Ru(CO)4(C2H4) + dppm

Ru(CO)4(κ1-dppm) + Os3(µ-H)2(CO)10

3 Ru(CO)4(C2H4)hν

Ru(CO)4(κ1-dppm) + C2H4

RuOs3(µ-H)2(CO)9(µ-CO)2(µ-dppm) + 3 CO

Ru

Eur. J. Inorg. Chem. 1585 15982007 -, , 11 ,

Activation of Hydrogen by an Unsaturated Pt-Os Cluster complexOs

ADAMS R.D.; CAPTAIN B.; ZHU L.

GN

PBu3

Os

Pt

Os

PBu3

Os

Pt

PBu3

Pt

Os

PBu3

PtH

Os OsH

PBu3

PBu3

PtH

Os

H

Os

H

Pt

Os

H

0°C+ H2

0°C+ H2

25°C- H2

25°C- H2

Preparation of unsaturated pentanuclear platinium-osmium cluster complex that can reversibly absorb large amounts of hydrogen

Pt

J. Am. Chem. Soc. 2454 24552007 129 -, , 9 ,

Design of Cytotoxic Anticancer Os(II) Arene ComplexesOs

PEACOCK A.F.A.; PARSON S.; SADLER P.J.

GN

R

N

OOs

X

Study of the hydrolitic and aqueous solution chemistry of half-sandwich Os(II) arene complexes that can be tuned with N,O-chelating ligands to achieve cancer cell cytotoxicity comparable to carboplatin

J. Am. Chem. Soc. 3348 33572007 129 -, , 11 ,

Osmium Catalyzed Asymmetric DihydroxylationsOs

Study on the hydrolysis step of osmium (mono)glycolates of styrenes

M.H. JUNTTILA, O.E.O. HORMI

CM

O

O

R

OsO

OL

(VI)

J. Org. Chem. 2956 29612007 72 -, , 8 ,

23

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

A Recyclable Osmate-Exchanged Chloroapatite CatalystOs

for Catalytic Asymmetric Dihydroxylation of Olefins

S.K. DEHURY, V.S. HARIHARAKRISHNAN

CM

RR'

RR'

OH

OH

yield: 71-96%ee: 90-97%

CAP-OsO4(DHQD)2PHAL

t-BuOH-H2ONMO, RT

Tetrahedron Lett. 2493 24962007 48 -, , 14 ,

Bis(indolyl)maleimide PyridinophanesCo

Bis(indolyl)maleimide pyridinophanes are potent selective inhibitors of glycogen synthase kinase-3.

ZHANG, H.-C.; BONAGA, L. V. R.; YE, H.; DERIAN, C. K.; DAMIANO, B. P.; MARYANOFF, B. E.

PL

N

HN

O O

N

N

HN

O O

N

N

NRR'

R = R' = Me or R, R' = (CH2)4

+ isomerRR'N-CN

CpCo(CO)21,4-dioxane

115-11°C, 24 h

9-12% yield

Bioorg. Med. Chem. Lett. 2863 28682007 17 -, , 10 ,

Cobalt Catalyzed Formation of Methylenecyclopentanol from Allene and EnoneCo

CHANG, H.-T.; JAYANTH, T. T. ; CHENG, C.-H.

PJF

R1

R2

OR

2

HR

1

OHCoI2(dppe)

Zn, ZnI2

CH3CN, H2O

+

R1 = Alkyl, ArR2 = Alkyl

60-90%

J. Am. Chem. Soc. 4166 41672007 129 -, , 14 ,

Cobalt Carbometallation of Norbornen with EthyleneCo

BIANCHINI, C.; GIAMBASTIANI, G.; MELI, A.; TOTI, A.

PJF

N

NCo

Cl Cl

Co catalyst

up to 97%rd > 99%

Catalsyt

methylaluminoxaneethylene

Organometallics 1303 13052007 26 -, , 6 ,

24

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Oligomerization of Ethylene by Cobalt(II) 6-(Thienyl)-2-(imino)pyridine CatalysisCo

EPR studies demonstrate a spin state changeover upon activation of the catalyst by MAO

BIANCHINI, C.; GATTESCHI, D.; GIAMBASTIANI, G.; RIOS, I.G.; IENCO, A.; LASCHI, F.; MEALLI, C.; MELI, A.;SORACE, L.; TOTI, A.; VIZZA, F.

AN

NBrO

NH2

MeOH reflHCOOH (cat.)

NBrN

S

SnMe3

Pd(PPh3)4

NNS

NNS Co

Cl Cl

CoCl2THF

Organometallics 726 7392007 26 -, , 3 ,

Kinetic Studies on the Cobalt-Catalyzed Norbornadiene Intermolecular PK ReactionCo

CABOT, R.; LLEDO, A.; REVES, M.; RIERA, A.; VERDAGUER, X.

AN

SiMeMe

Me+

Co2(CO)8 cat.

∆, CO

H

H

O

TMS

Organometallics 1134 11422007 26 -, , 5 ,

Synthesis of 4-(Cyclopropylmethylene)cyclopentenonesCo

6 examples, yields: 43-59%; Pauson-Khand reactions with allenes.

AHMAR, M.; KNOKE, M.; DE MEIJERE, A.; CAZES, B.

GJ

Et

Et

Co2(CO)

6

O

Et

Et

+NMO, 0-20°C

CH2Cl2, THF

54%(Z/E 5:95)

Synthesis 442 4462007 -, , 3 ,

Continuous Enantioselective Kinetic Resolution of Terminal EpoxidesCo

Jacobsen’s cobalt-salen complex covalently linked on polymer carriers; continuous-flow reaction.

SOLODENKO, W.; JAS, G.; KUNZ, U.; KIRSCHNING, A.

GJ

OH O O

OH

(CF3)3COH linkerCo

t-BuO

t-B u

N

O

t-Bu

N

OAc

+

catalyst(2.8 mol%)

(0.2 equiv)(5 equiv))

THF, rt

93% (ee 95.5%)

catalyst

Synthesis 583 5892007 -, , 4 ,

25

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Regioselective Ring-Opening in Hexopyranosides Co

TANI, S.; SAVARDI, S. KOJIMA, M.; AKAI, S.; SATO, K.-I.

GP

O

O

O X

OROR'

Ph

OH

O

O X

OROR'

Ph

CoCl2 (3 eq.)

BH3.THF (3 eq.)THF, r.t., 10 min.

6 examples85%-quant.

Tetrahedron Lett. 3103 31042007 48 -, , 17 ,

Catalysed Substitutive Arylation of cis-Allylic Diols with ArylboroxinesRh

Asymmetric version (41 - 87 % ee) developed with BINAP or Carreira’s chiral diene.

MIURA, T.; TAKAHASHI, Y.; MURAKAMI, M.

AF

OHHO + (ArylBO)3

[Rh(OH)(cod)]2(2.5 mol %)

dioxaner. t., 12 h

HO

Ar(3 equiv.)

22 - 81 %

Ar: 4-Me-C6H4, 4-F-C6H4, 3-MeO-C6H4, 1-naphtyl, PhCHCHCH2

Chem. Commun. 595 5972007 -, , 5 ,

(1-Phosphanylferrocen-1’- and -2-yl)methyl-Linked Diamino Ruthenium CarbeneRh

LABANDE, A.; DARAN, J-C.; MANOURY, E.; POLI, R.

DL

PPh2

NN

R

1) t-BuOK, [Rh(COD)Cl]2THF

2) NaBF4, DCM/H2O, rtor AgBF4, DCM, rt.

Ph2P

N N R

Rh

+

75-81% yield

NN

R

1) t-BuOK, [Rh(COD)Cl]2THF

2) NaBF4, DCM/H2O, rtor AgBF4, DCM, rt.

+PPh2

NN

RPh2PRh

77% yieldR: Me, 2,4,6-Me3C6H2

FeBF4

- Fe

BF4-

Fe

BF4-

BF4-

Fe

Eur. J. Inorg. Chem. 1205 12092007 -, , 9 ,

Rhodium(I) Complexes Containing ββββ-Amino Alcohol and 1,2-Diamine LigandsRh

DAHLENBURG, L.; TREFFERT, H.; FARR, C.; HEINEMANN, F. W.; ZAHL, A.

DL

[(η4-C8H12)2Rh2(µ-Cl)2]

NH

RhCl

+

H2NOH

iPrOH

iPr KOH RhNH

O

iPr

Eur. J. Inorg. Chem. 1738 17512007 -, , 12 ,

26

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Rh-Catalysed Asymetric HydrogenationRh

22 exemples are described.

DARCEL, C.; MOULIN, D.; HENRY, J-C.; LAGRELETTE, M.; RICHARD, P.; HARVEY, P. D.; JUGÉ, S.

DL

Ph

MeO2C NHCOMe H2, solvent

[Rh(COD)L]+BF4-

Ph

MeO2C NHCOMeH

ONMe

PhMe

P R3R2

PPhR1

L:

R1: Ph, o-An, o-MEMPh, 1-Np, Fc, 2-Np, o-biPh, t-Bu, Me, C6H11

solvent: C6H6, DCM, MeOH, i-PrOH, EtOH

R2, R3: OPh, Ph, o-An

60-99% yield1-99% ee

Eur. J. Org. Chem. 2078 20902007 -, , 13 ,

Sequential Silylcarbocyclization / Cross-Coupling of EnynesRh

DENMARK, S. E., LIU, J. H.

CJM

XR

YX

Y

R

SiMe2BnX

Y

R

ArR= H, MeX= CE2, NBn, OY= H, CO2Et

HSiMe2BnRh4(CO)12

CO (1 Atm)hexane

TBAF 2 Eq.Ar-IPd2dba3 2.5%

THF, rt

PdSi

J. Am. Chem. Soc. 3737 37442007 129 -, , 12 ,

Synthesis of Functionalized Arenes Through Rh(I)-Catalyzed [2+2+2]CycloadditionRh

CLAYDEN J.; WESLEY J. M.

AE

R1

X

R1

R2

R1

R1

R2X10 mol% Rh(cod)2BF410 mol% rac-BINAP

yield : 56 to 93%X = C(CO2Me)2, O, NTsR1 = Me, Et, PhR2 = H, Me, OMe

Org. Biomol. Chem. 1028 10302007 5 -, , 7 ,

Base-Promoted Selective Activation of Benzylic C-H Bonds of Toluenes by Rhodium(III)Porphyrins

Rh

CHAN, K.S.; CHIU, P.F.; CHOI, K.S.

AN

Rh(ttp)Cl +

FG

CH3

10 equiv. base

120°C, N 2

FG

Rh(ttp)ttp = tetrakis-(4-tolylporphyrin)

FG = OMe, 92% tBu, 98% Me, 90% 3,5-Me2, 45% H, 90% F, 97% CN, 83% NO2, 98%

Organometallics 1117 11192007 26 -, , 5 ,

27

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Reactivity of Rhodium(I) Iminophosphine Carbonyl Complexes with Methyl IodideRh

BEST, J.; WILSON, J.M.; ADAMS, H.; GONSALVI, L.; PERUZZINI, M.; HAYNES, A.

AN

Rh

I

P

N

CO

Rh

I

P

N

CO

Rh

I

P

N

Ik1 MeI

k-1

k2

k-2

Me

I

COMe

Ph2P N

R1

R3R5

R4R2

PN=

Organometallics 1960 19652007 26 -, , 8 ,

Activation of Aldehydic Carbon-Hydrogen Bonds under Aerobic Conditions by MaskedRhodium(III) Porphyrin Cation

Rh

high yields of Rh(ttp)COR under anaerobic or aerobic conditions have been reached

CHAN, K.S.; LAU, C.M.; YEUNG, S.K.; LAI, T.H.

AN

Rh(ttp)CH2CH2OH

FGOHC

THF, 50°CFG

(ttp)Rh

O

ttp = tetrakis-(4-tolylporphyrin)

Organometallics 1981 19852007 26 -, , 8 ,

Phenols from CyclobutenonesRh

A mechanism via ketene formation is proposed.

KONDO, T.; NIIMI, M.; NOMURA, M.; WADA, K.; MITSUDO, T.-A.

GP

R

R

OR'

O

R

R

OH

R'

O

+

RhCl(C2H4)2 (5%)

P(c-C6H11)3, 10%toluene, 130°C, 12h

5 examples40-65%

Tetrahedron Lett. 2837 28392007 48 -, , 16 ,

Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes Ir

Several examples are reported on the preparation of axial chiral compounds.

SHIBATA, T.; ARAI, Y.; TAKAMI, K.; TSUCHIKAMA, K.; FUJIMOTO, T.; TAKEBAYASHI, S.; TAKAGI, K.

AF

NapZ

Nap

OH

OHNap = 1-naphtylZ = O, NTs, CH2

ZOHOH

43 - 98 %

99% ee

[Ir(cod)Cl]2 (10 mol %)(S,S)-MeDUPHOS (20 mol %)

xylener. t. or reflux

2 - 72 h

+

Adv. Synth. Catal. 2475 24832007 348 -, , 16-1

,

28

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

2,4-Dimethylpentane Dyads and 2,4,6-Trimethylheptane Triads PreparationIr

ZHOU, J.; BURGESS, K.

AF

TBDPSO

OH

TBDPSO OH

syn/antiD-1 12:1L-1 1:6

"Ir"(1 mol %)

+ H250 atm CH2Cl2

25 °C, 4 h O N

N

NIr

PriPr

i(cod)

+BArF-L-1:

Angew. Chem. Int. Ed. 1129 11312007 46 -, , 7 ,

Ir(III) Tolylterpyridine Complexes: Synthesis, Characterization and DFT studiesIr

Physical properties are provided

YOSHIKAWA, N.; YAMABE, S.; KANEHISA, N.; KAI, Y.; TAKASHIMA, H.; TSUKAHARA, K.

DL

(NH4)3[IrCl6]+

tterpy

1) ethylene glycol

mW, 3min2) L, 12min

3) KPF6 aq.sat.

IrN N

NN

N

Clif L=dmbpy

63% yieldlight yellow

L: Phen, dpphen, bpy,

Eur. J. Inorg. Chem. 1911 19192007 -, , 12 ,

Catalyzed Coupling of Alkenes and Aldehydes Ni

HO, C.-H.; JAMISON, T.F.

AF

R1+ R2-CHO R

1R2

OSiEt3

Ni(cod)2 (20 mol %)I (20 mol %)

P(OPh)3 (20 mol %)

Et3SiOTf, NEt3toluene up to 99%

N N

iPr

iPr

Pr

Pr

i

i

I:

Angew. Chem. Int. Ed. 782 7852007 46 -, , 5 ,

Carbocyanation of AlkynesNi

The Lewis acid has a dramatic effect on the reaction outcome.

NAKAO, Y.; YADA, A.; EBATA, S.; HIYAMA, T.

GP

R'

Ar

R R'

CNArCN + R

Ni(cod)2 (1%)-PMe3 (4%)AlMe3 (4%)

toluene, 80°C

17 examples78-94%

AlB

J. Am. Chem. Soc. 2428 24292007 129 -, , 9 ,

29

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

The Mechanism of Polymerization of Butadiene by “Ligand-Free” Ni(II) ComplexesNi

O’CONNOR, A. R.; WHITE, P. S.; BROOKHART, M.

MVI

CH3

Ni

F3C CF3

B(ArF)3 CH3

Ni

CD2Cl2

CH3

Ni

-63°C

-110°C

J. Am. Chem. Soc. 4142 41432007 129 -, , 14 ,

Role of Styrene in Nickel-Catalyzed Anhydride Cross-CouplingNi

Effect of styrene was demonstrated in both system

JOHNSON, J. B.; BERCOT, E. A.; ROWLEY, J. M.; COATES, G. W.; ROVIS, T.

MVI

O

O

O

H

H

Ni(COD)2

Et2Zn

Et

O

OH

O

H

H

O

O

O

Ni(COD)2

Et2ZnO

Et

O

OH

PPh2

N

Obipy

4-F-styreneiPrPHOXstyrene

iPrPHOX

Rate LimitingReductive Elimination

Rate LimitingOxidative Addition

J. Am. Chem. Soc. 2718 27252007 129 -, , 9 ,

Ni(0)-Promoted HydroxycarboxylationNi

AOKI, M.; IZUMI, S.; KANEKO, M.; UKAI, K.; TAKAYA, J.; IWASAWA, N.

CC

CR

R R

R

1

2

3

4R

R

R

ROH

COOMe

1

2

3

4

RR

R

RHOCOOMe1

2

3 4

i) CO2 (1 atm), dtbpy (1.1 eq), Ni(cod)2 (1 eq), THF, 0°C, 2hii) HCl/MeOH, -78°C then O 2, -78°C, 2h

iii) Me2S, 0°Civ) TMSCHN2, MeOH, 0°C

+

8 ExamplesYields = 44 - 82%

R1, 2, 3, 4 = H, alkyl, cycloalkyl, Ph, CH2CH2Ph

Org. Lett. 1251 12532007 9 -, , 7 ,

Pd-Catalyzed Hydrogenolysis of Benzylic Nitro GroupPd

This represent new opportunities in asymmetric synthesis

FESSARD, T.C.; MOTOYOSHI, H.; CARREIRA, E.M.

CY

Ar

NO2

*Ar *

Pd(OH)2/C (5-10 mol%), EtOH, H2 (1 bar), 70 °C

many examples, 50-95%

Angew. Chem. Int. Ed. 2078 20812007 46 -, , 12 ,

30

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Borosalicylic Acid: an Advantageous Promoter for the Methoxycarbonylation of Ethylene Pd

FERREIRA, A.C.; CROUS, R.; BENNIE, L.; MEIJ, A.M.M.; BLANN, K.; BEZUIDENHOUDT, B.C.B.; YOUNG, D.A.; GREEN,M.J.; ROODT, A.

CY

+ CO + MeOH

Pd(OAc)2, PPh3,B(OH)3, salicylic acid

O

OMe

Angew. Chem. Int. Ed. 2273 22752007 46 -, , 13 ,

Three-Component Cross-Coupling of Aryl Halides, Alkynes and ArynesPd

Various polycyclic aromatic compounds are prepared

LIU, Z.; LAROCK, R.C.

CY

R1

I

R2 R3 R4 R4

R2

R3

R1

Pd(dba)2 (5 mol%), CsF (3 equiv),TlOAc (1.2 equiv),1:1 MeCN:toluene, 90 °C, 8 h

++56-91%

Angew. Chem. Int. Ed. 2535 25382007 46 -, , 14 ,

Substituted 2-Pyridylmethyl from Aromatic Halides and 2-(2-Pyridyl)-ethanolPd

NIWA, T.; YORIMITSU, H.; OSHIMA, K.

CY

Cl

ClCl

N

N

N

Pd(OCOCF3)2 (15 mol%)PCy3 (30 mol%)

Cs2CO3 (3.6 equiv)xylene, reflux, 10 hNOH

iPriPr+ 3

81%

Angew. Chem. Int. Ed. 2643 26452007 46 -, , 15 ,

Alcohols Oxidation Catalyzed by Palladium in Carbon WallsPd

LU, A.-H; LI, W.-C.; HOU, Z.; SCHÜTH, F.

BJL

RCH2OHPd/OMC

OMC : ordered mesoporous carbon

80-100°C

RCHO RCH2OH : benzyl alcohol 1-phenylethanol, cinnamyl alcohol

selectivity >99%

Chem. Commun. 1038 10402007 -, , 10 ,

31

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Synthesis of Substituted Benzene Fused with Carbocycles and HeterocyclesPd

SWAMY, N. K.; TATINI, L. K.; BABU, J. M.; ANNAMALAI, P.; PAL, M.

BJL

OI PdCl2(PPh3)2 cat

80°C+ RH

O

R

R

50-80%

Chem. Commun. 1035 10372007 -, , 10 ,

Synthesis of the First Pyrazolin-4-ylidene Complexes of Palladium(II)Pd

HAN, Y.; HUYNH, H. V.

BJL

R1 R1

OO

1. R2NHNH22. KI/I23. EtI

NN

I+

I-R2

1. Pd2(dba)3, PPh32. AgO2CCF3

NN

Pd+

R2O2CCF3

PPh3

O2CCF3

Chem. Commun. 1089 10912007 -, , 10 ,

Synthesis and Reactivity with Amines of Alkylpalladium N-Heterocyclic CarbenePd

The factors that might be barriers to the Pd-catalyzed alkyl-amination is discussed

ESPOSITO, O.; LEWIS, A. K. K.; HITCHCOCK, P. B.; CADDICK, S.; CLOKE, F. G. N.

BJL

Pd

N

N

t-Bu

t-Bu Pd

N

N

t-Bu

t-BuCl

Cl

RR'NHPd NHRR'ClN

N

t-Bu

t-Bu

RR'NH : morpholine hexylamine

Chem. Commun. 1157 11592007 -, , 11 ,

Magnetic Pd Nanoparticles for C-C Bond FormationPd

Suzuki and Sonogashira coupling are also presented

YOON, H.; KO, S.; JANG, J.

BJL

Pd nano (cat)3.8 nm

2 recycling

I

+

97%

Chem. Commun. 1468 14702007 -, , 14 ,

32

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

9-Fluorenylphosphines for Pd Cross-Coupling ReactionsPd

FLECKENSTEIN, C. A.; PLENIO, H.

MF

ClR R

1 % [Pd] / 2 % L0.75 % CuI

DMSO, 100-120 °C

PR2H+

BF4-

L : 9-Fluorenylphosphines

Chem. Eur. J. 2701 27162007 13 -, , 9 ,

Sugar-Based Ligand for Asymmetric Pd-Catalyzed Heck ReactionsPd

MATA, Y.; PAMIES, O.; DIÉGUEZ, M.

MF

O

O

OTf

O

O

[Pd] / L

MW / 70 °C

high ee, high conversion

OO

O

N O

R

OP

O O

Ph

L : Phosphite–Oxazoline

Chem. Eur. J. 3296 33042007 13 -, , 12 ,

N-Type Conjugated Materials Through Heck ReactionPd

Promising candidates for use as organic solar cells

SHIN, R. Y. C.; KIETZKE, T.; SUDHAKAR, S.; DODABALAPUR, A.; CHEN, Z.-K.; SELLINGER, A.

MVI

N N

CNNC

RAr BrBr

N

NNC

NC

RAr

N

N CN

CN

R+

2% [Pd(P(t-Bu)3)2]

2.5 equiv. Cy2NMe

DMF, 80°C

Chem. Mater. 1892 18942007 19 -, , 8 ,

Coordination Constants of Differents Ligands based on a Pd Pincer ComplexPd

MINAKAWA, M.; TAKENAKA, K.; UOZUMI, Y.

MF

Pd

Cl

NNPh

HaHa

Ph

HaHa

Hb Hb

Pd

Cl

NNPh

HaHa

Ph

HaHaHb HbL L

L

L : P-coordinating ligands, As-coordinating AsPh3, N-coordinating pyridine

Eur. J. Inorg. Chem. 1629 16312007 -, , 12 ,

33

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Ionic Liquid Effect in Buchwald-Hartwig Amination R eactionPd

MCNULTY, J.; CHEEKOORI, S.; BENDER, T. P.; COGGAN, J. A.

BJL

Br + NHPd(0) cat / PR3 cat

t-BuONa, IL, ∆N IL : trialkylphosphonium salt

72-75 %

Eur. J. Org. Chem. 1423 14282007 -, , 9 ,

Ligand-free Suzuki ReactionPd

DENG, C.-L.; GUO, S.-M.; XIE, Y.-X.; LI, J.-H.

BJL

XR1

B(OH)2R2

+Pd(OAc)2 cat

MeONa, rt R1 R2

9-99%

Eur. J. Org. Chem. 1457 14622007 -, , 9 ,

Stereoselective Oxazine FormationPd

JOO, J.-E.; LEE, K.-Y.; PHAM, V.-T.; HAM, W.-H.

BJL

R

NHBz

OTBS

ClPd(0) cat

Base, n-Bu4NIN O

Ph

R

OTBS

59-89%syn/anti 14/1-1/16

Eur. J. Org. Chem. 1586 15932007 -, , 10 ,

Buchwald-Hartwig Coupling of Aminothiophenes with HalopyridinesPd

BEGOUIN, A.; HESSE, S.; QUEIROZ, M.-J. R. P.; KIRSCH, G.

BJL

SNH2

R2

R1

CO2Me

+NX R Cs2CO3, ∆

X = I, Br, ClR = H, X

SNH

R2

R1

CO2Me

N

R13-73%

Eur. J. Org. Chem. 1678 16822007 -, , 10 ,

34

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Bromo-Cyano-Substituted Azulene Building Block for Acetylenic ScaffoldingPd

PETERSEN, M. Å.; KILSÅ, K.; KADZIOLA, A.; NIELSEN, M. B.

BJL

NC CNPh Ph

NC

Br

Pd(II) catt-Bu3P, CuI

SiMe3

NHi-Pr2

Ph

NC

SiMe3

1. Base2. Cu(I) cat

79% 27%

PhNC

2

Cu

Eur. J. Org. Chem. 1415 14182007 -, , 9 ,

Carbonylative Suzuki-Miyaura for the Synthesis of Unsymmetrical DienonesPd

BARTALI, L.; GUARNA, A.; LARINI, P.; OCCHIATO, E. G.

BJL

X OTf B(OH)2R1

R2+

Pd(OAc)2 5%, PPh3 10%

CO (1atm), base, THF XO

R1

R2

31-83%

B

Eur. J. Org. Chem. 2152 21632007 -, , 13 ,

Imidazolium-Based Ionic Liquid for Heck ReactionsPd

The catalyst was reused six times

IRANPOOR, N.; FIROUZABADI, H.; AZADI, R.

BJL

XR1

+ R2PdCl2 (cat), IL

NEt3, ∆

R1 R2

IL:NN

PF6

OPPh2

60-97%X = Cl, Br, I

Eur. J. Org. Chem. 2197 22012007 -, , 13 ,

Enantioselective Cyclization of Silyloxy 1,6-EnynesPd

CORKEY, B. K.; TOSTE, F. D.

CJM

I

Me

OTBS ((R)-DTBM-Segphos)Pd(OTf)2 10%

96% yield, 95% ee

OI

Me

J. Am. Chem. Soc. 2764 27652007 129 -, , 10 ,

35

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Methylation and Arylation of C-H Bonds in Carboxyli c AcidsPd

Ortho methylation and arylation of benzoic acids are also described

GIRI, R.; MAUGEL, N.; LI, J.; WANG, D.; BREAZZANO,S. P.; SAUNDERS, L. B.; YU, J.

CJM

R COOHMe Me

+ Ar BO

OPd(OAc)2 10%Benzoquinone

Ag2CO3, K2HPO4t-BuOH, 100 °C

R COOHMe

Ar

J. Am. Chem. Soc. 3510 35112007 129 -, , 12 ,

Enantioselective Desymetrization Using a C-C Bond CleavagePd

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

CJM

B(pin)Ph2MeSi +

R

R

R

R

SiMePh2

B(pin)

5 examples50-95% yield81-91% ee

Pd(dba)2 2%L* 2.4%

toluene, 50 °C

PAr3L*=

SiB

J. Am. Chem. Soc. 3518 35192007 129 -, , 12 ,

Dialkoxylation of 2-Propenyl PhenolsPd

ZHANG, Y.; SIGMAN, M. S.

CJM

R2

OHR1

Pd(MeCN)2Cl2 10%Quinox 12%

O2, ROH, 3Årt

R2

OHR1

OR

ORR2

OPdCl

ORR1

H

J. Am. Chem. Soc. 3076 30772007 129 -, , 11 ,

Total Synthesis of Marcfortine B via a TMM CycloadditionPd

TROST, B. M.; CRAMER, N.; BERNSMANN, H.

CJM

NBoc

OMeOMe

O +

TMS

TMS

OCO2Me

OMeOMeN

Boc

O

HO2CPd(OAc)2 5%P(O-i-Pr)3 35%

toluene, reflux

93%

J. Am. Chem. Soc. 3086 30872007 129 -, , 11 ,

36

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Carbocyclic Carbene LigandsPd

Low (8.10-5 mol %) catalyst loadings are described for Heck reactions

YAO, Q.; ZABAWA, M.; WOO, J.; ZHENG, C.

CJM

R R

PdNO

OAc

J. Am. Chem. Soc. 3088 30892007 129 -, , 11 ,

Monophosphine-Based Catalysts for Suzuki-Miyaura Reactions on HeteroaromaticsPd

Efficient ligands for the Suzuki-coupling of boronic derivatives with heteroaryl-halides

BILLINGSLEY, K.; BUCHWALD, S. L.

CJM

PCy2MeO OMe

PCy2i-Pr

i-Pr

i-Pr

J. Am. Chem. Soc. 3358 33662007 129 -, , 11 ,

Kumada-Corriu Cross-Coupling Reactions with Knochel-type Grignard ReagentsPd

MARTIN, R.; BUCHWALD, S. L.

CJM

PCy2Me2NR1

I+ R2

MgX

R1R2

Pd(dba)2 2%L 3%

Toluene / THF-20 °C

L=

21 examples

Mg

J. Am. Chem. Soc. 3844 38452007 129 -, , 13 ,

Total Synthesis of 2’-O-Methylmyxalamide DPd

COLEMAN, R. S.; LU, X.; MODOLO, I.

CJM

HO NH

OOMe

Stille-Coupling Suzuki-CouplingBSn

J. Am. Chem. Soc. 3826 38272007 129 -, , 13 ,

37

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Polymerization of CO/ethene: DFT studiesPd

Steric bulk and wide bite angles favors ester formation over polymerization

ZUIDEMA, E.; BO, C.; VAN LEEUWEN, P. W. N. M.

CJM

PPd

P

OC H

CO /

O

OVs.

O

nmethanol

J. Am. Chem. Soc. 3989 40002007 129 -, , 13 ,

Allylation of Aldehydes with Vinyl EpoxidePd

KIMURA, M.; MUKAI, R.; TAMAKI, T.; HORINO, Y.; TAMARU, Y.

CJM

R1 R2

OO

R1 R2

O

OH

Pd(acac)2nBu3PEt3B

R1R2

HO

THF 50 °CPd(Ph3P)4DMSO, rt

J. Am. Chem. Soc. 4122 41232007 129 -, , 14 ,

Decarboxylative Coupling of Heteroaromatic AlkanesPd

WAETZIG, S. R.; TUNGE, J. A.

CJM

HetAr

R1O

O

R2Pd(Ph3P)4 5%

toluene, 100 °C

HetAr

R1

R2R3 R316 examples30-95% yields

J. Am. Chem. Soc. 4138 41392007 129 -, , 14 ,

Insertion of Oxygen into a Palladium-Hydride BondPd

The two pathways are isoenergetic

POPP, B. V.; STAHL, S. S.

CJM

AcO PdII

NHC

NHC

HO2

AcO PdII

NHC

NHC

H OO

vs. PdII

O

ONHC

NHCAcO PdII

NHC

NHC

OOH

J. Am. Chem. Soc. 4410 44222007 129 -, , 14 ,

38

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Allylation of Aryl Halides via a Retro-AllylationPd

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

CJM

R2

OH

R5R1

R6R7

R3 R4

+ Ar-X

Pd(OAc)2 / PCy3Cs2CO3

toluene, reflux

R6ArR7

R3

R4R5

J. Am. Chem. Soc. 4463 44692007 129 -, , 14 ,

Bicycles via a Cyclization-Oxidation SequencePd

TONG, X.; BELLER, M.; TSE, M. K.

CJM

R

O X

Pd(OAc)2 10%

2 Eq. PhI(OAc)2AcOH X

OO

R8 examplesR= O, NTs51-83%

J. Am. Chem. Soc. 4906 49072007 129 -, , 16 ,

Asymmetric Allylic Trichloroacetamidate Rearrangement.Pd

A model (DFT studies) for enantioinduction is discussed

WATSON, M. P.; OVERMAN, L. E.; BERGMAN, R. G.

CJM

O NH

CCl3

R R

NH

CCl3

OPdL*

J. Am. Chem. Soc. 5031 50442007 129 -, , 16 ,

Intramolecular C-H Activation via an Aryl to Imido yl Palladium MigrationPd

ZHAO, J.; YUE, D.; CAMPO, M. A.; LAROCK, R. C.

CJM

N

I

ZR1 R2

Z

O

R1 R2

Pd(OAc)2 5%dppm 5%CsPiv 2 Eq.

DMF, 100 °C

J. Am. Chem. Soc. 5288 52952007 129 -, , 16 ,

39

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Total Synthesis of (-)-TerpestacinPd

TROST, B. M.; DONG, G.;VANCE, J. A.

CJM

O

OHO+

Pd2dba3 CHCl3 1%Trost L* 2.6%Bu4NCl 50%

DCM95% yield, 96% ee

O

OOH

O

HO

HOOH

J. Am. Chem. Soc. 4540 45412007 129 -, , 15 ,

Decarboxylative Cross-Coupling ReactionsPd

GOOSSEN, L. J.; RODRIGUEZ, N.; MELZER, B.; LINDER, C.; DENG, G.; LEVY, L. M.

CJM

Ar OH

O

+

X

R

Ar

R + CO2

Pd(acac)2 2%P(i-Pr)Ph2 6%CuCO3, KFNMP, 120 °C

Pd(acac)2 1%CuI 3%Phenanthroline 5%K2CO3NMP,160 °C

or

Cu

J. Am. Chem. Soc. 4824 48332007 129 -, , 15 ,

Palladium-Catalyzed Formal [4+2] Cycloaddtion of o-Xylylenes with OlefinsPd

KUWANO, R.; SHIGE, T.

VM

SiMe3OCO2Me EWG

R

Pd(η3-C3H5)Cp (3 mol%)dppe (3.3 mol%)

DMSO, 120°C

R

EWG

47-92% Yield

Si

J. Am. Chem. Soc. 3802 38032007 129 -, , 13 ,

Synthesis of Alkynylpyrimidine Amide DerivativesPd

~ 20 exemples; tested as inhibitors of Tie-2 Kinase.

CEE, V.J.; ALBRECHT, B.K.; GEUNS-MEYER, S.; HUGHES, P.; BELLON, S.; BREADY, J.; CAENEPEEL, S.; CHAFFEE,S.C.; COXON, A.;EMERY, M.; FRETLAND, J.; GALLANT, P.; GU, Y.; HODOUS, B.L.; HOFFMAN, D.; JOHNSON, R.E.;

GJ

N

NNH2

O

NH

I

CF3 N

N

NH2

O

NH

CF3

Pd(PPh3)2Cl

2

+

2 equiv

(5 mol%)

CuI (5 mol%)

MeCN, Et3N, 80°C

69%

Cu

J. Med. Chem. 627 6402007 50 -, , 4 ,

40

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Pd-Catalyzed Synthesis of N-aryl-3-arylmethylisoxazolidinesPd

PENG, J.; LIN, W.; YUAN, S.; CHEN Y.

MV

ONH2

R

1 mol% Pd2dba32 mol% Xantphos

2.4 equiv. NaOt-Butoluene, 90°C, 3h

42-82%R = Ar, i-Pr

+ Ar-Br ONAr

R

Ar

Na

J. Org. Chem. 3145 31482007 72 -, , 8 ,

Heck Arylations of Allyl Alcohols in Ionic LiquidsPd

CALO, V.; NACCI, A.; MONOPOLI, A.; FEROLA, V.

MV

1.2 mol% Pd(OAc)2

TBAB, NaHCO370-1300C, 60-92%

R'

OH

R + Ar-X

X = Br, I

R'

O

R

Ar+

R'

O

R

Ar

1.2 mol% Pd(OAc)2

TBAA

R'

OH

Ar

R+

R'

OH

Ar

R

70-1300C, 60-92%

Na

J. Org. Chem. 2596 26012007 72 -, , 7 ,

Pd-Catalyzed N-arylation of Heterocyclic DiaminesPd

CABELLO-SANCHEZ, N.; JEAN, L.; MADDALUNO, J.; LASNE, M.-C.; ROUDEN, J.

MV

NH

+ Ar-Br

NH2

n

m

Cond.

n = m = 168%

NPh

NH2

Cond.

n = 1, m = 262%N

H

HNO Cond. = Pd2dba2 (1 mol%), BINAP (1.5 mol%)

NaOt-Bu (1.4 equiv.)toluene, 110°C, 24h

Na

J. Org. Chem. 2030 20392007 72 -, , 6 ,

Pd-Catalyzed C-P Coupling Reactions Between Vinyltriflates and Phosphine-BoranesPd

JULIENNE, D.; LOHIER, J.-F.; DELACROIX, O.; GAUMONT, A.-C.

MV

OTf

R2

R1

R1

+ PH

BH3

R3R4

5.6 mol% dpppPdCl2

K2CO3, DMSO60°C, 75-90%

P

R2

R1

R1

R3

R4

BH3R1 = H, Ph, MeR2 = Me, t-Bu, HR3 = Me, Et, CyR4 = Ph, Me, Et, Cy

K

J. Org. Chem. 2247 22502007 72 -, , 6 ,

41

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Synthesis of 4-AminoquinolinesPd

MARGOLIS, B.J.; LONG, K.A.; LAIRD, D.L.T.; RUBLE, J.C.; PULLEY, S.R.

MV

4 mol% Pd(OAc)28 mol% DPEphos

dioxane, 85°C32-88%

+ Ar-BrR2HN NH2

R'N

NH

R'

R2HN

Y

XR = Me, EtR' = MeX = Cl, NO2Y = H, SMe, OMe, Br, CN, CO2Me, F

J. Org. Chem. 2232 22352007 72 -, , 6 ,

Cross-Coupling of 1,1-Dichloro-1-alkenes with 9-Alkyl-9-BBNPd

LIRON, F.; FOSSE, C.; PERNOLET, A.; ROULLAND, E.

MV

R

2.5 mol% Pd2dba35 mol% Xantphos

THF, refluxKF-K3PO4 or CsF-Cs2CO3

58-88%R = Ar, cyclopropyl, alkylR' = Bn, pentyl, CH2OBn

Cl

Cl

+B R'

R

Cl

R'KCs

J. Org. Chem. 2220 22232007 72 -, , 6 ,

Pd/C Redox Reactions between Aliphatic Secondary Alcohols ad KetonesPd

ESAKI, H.; OHTAKI, R.; MAEGAWA, T.; MONGUCHI, Y.; SAJIKI, H.

MV

R

OH

R'

10% Pd/CH2

D2O, ∆R

O

R'

R, R' = alkyl

CuK

J. Org. Chem. 2143 21502007 72 -, , 6 ,

Palladacycle as Catalyst for Ring Opening of Oxabicyclic Alkenes.Pd

Palladacycle as highly efficient catalyst for oxabicyclic opening with organozinc halides is reported.

ZHANG, T-K.; YUAN, K.; HOU, X-L.

AM

O

R1R2

R2R1

R3 R1R2

R2R1

OH

toluene, 80 °C

ArCH2ZnBr, palladacycle A (0.05 mol%)R3

ArPd

N

BrPh3P

OA :

58-80% yields

J. Organomet. Chem. 1912 19192007 692 -, , 10 ,

42

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Synthesis of 4-Arylpiperidines from 1-Benzyl-4-piperidonePd

MORRILL, C.; MANI, N. S.

CS

N

R

BnN

Si

Bn

Me Me

Bn

H Cl

N

R

Bn

R-Br (1.5 equiv)TBAF (4 equiv)

PdBr2-2[2-(t-Bu2P)biphenyl](5 mol%)

THF, 50°C, 20h

R-I (1.5 equiv)TBAF (4 equiv)

Pd2dba3-CHCl3(2 mol%)

THF, rt or 50°C, 18-20h45-99%(R = aryl)64-99%

(R = aryl)

Org. Lett. 1505 15082007 9 -, , 8 ,

Aminomethylations via Cross-Coupling ReactionPd

2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl = XPhos

MOLANDER, G. A.; SANDROCK D. L.

CS

NR1

R2BF3K Br

R+ RNR1

R2

Pd(OAc)2 (3% mol)XPhos (6% mol)

Cs2CO3 (3 eq.)solvent, heat 10 examples, 66-83% yield

B

Org. Lett. 1597 16002007 9 -, , 8 ,

Enantioselective Synthesis of P-Stereogenic Benzophospholanes2007

Pd

BRUNKER, T. J.; ANDERSON, B. J.; BLANK, N. F.; GLUECK, D. S.; RHEINGOLD, A. L.

CS

I

PE

PhH P

PhE

cat. "Pd(Me-DuPhos)"

NaOSiMe3 (E = lone pair)or proton sponge (E = BH3)

59-70% ee

Org. Lett. 1109 11122007 9 -, , 6 ,

Arylation of Electron-Rich HeterocyclesPd

BuAd2P = butyldi-1-adamantylphosphine, No copper additives are needed.

CHIONG, H. A.; OLAFS DAUGULIS, O.

CS

N

N

NH

NOMe

Me

ArCl, Pd(OAc)2

NMP, K3PO4BuAd2P

N

N

NH

NOMe

MeMe

86%

Org. Lett. 1449 14512007 9 -, , 8 ,

43

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Pd-Catalyzed anti-Hydrothiolation of 1-AlkynylphosphinesPd

KONDOH, A.; YORIMITSU, H.; OSHIMA, K.

CS

PR22R1

R3SH

+R1 H

R3S PR22

cat. Pd(OAc)2

EtOH, 25°C, 1-4h

15 examples, 55-93% yield

Org. Lett. 1383 13852007 9 -, , 7 ,

Highly Efficient Ruthenium Catalysts forthe Formation of Tetrasubstituted

Pd

STEWART, I. C.; UNG, T.; PLETNEV, A. A.; BERLIN, J. M.; GRUBBS, R. H.; SCHRODI, Y.

CS

X

MeMe

n

X = C(CO2R)2, n = 1,2X =NTs, n = 1X= O, n = 1

X

n

MeMe

N N

Cl2Ru

Oi-Pr

0.1 M, C6H6, 60°C

> 95% conversion5- and 6-membered rings

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Cyanation of ArCl.Pd

Other similar ligands have been synthesised. Various bases and solvents tested. 13 examples.

CHENG, Y.-N.; DUAN, Z.; LI, T.; WU, Y.

MJ

ArCl

cat. (0.02 equiv.)

K4[Fe(CN)6].3H2O (0.22 eq.)

Na2CO3 (1 eq.)NMP, 140 °C, 18 h

ArCN81%

cat. :

Pd

N

Fe

ClPCy3

OEt

Fe

Synlett 543 5462007 -, , 4 ,

Three-Component Coupling.Pd

Various ligands and solvents tested. 8 examples.

YOSHIDA, M.; MURAO, T.; SUGIMOTO, K.; IHARA, M.

MJ

O

Ph

OH

OO

O

O

Ph

+

Pd2(dba)3.CHCl3 (0.05 eq.)

dppp (0.2 eq.)

dioxane, 50 °CMS 3Å

70%

+ CO2(1 atm.)

(1.2 eq.)

Synlett 575 5782007 -, , 4 ,

Coupling-Cyclization Procedure.Pd

Also with allylCl. 11 examples.

MA, S.; YU, F.; ZHAO, J.

MJ

C4H9

POH

OEtO

PdCl2(PhCN)2 (0.05 eq.)

DMF, 80 °C, 2 h

72% OP

C4H9

OEt

O

Br+

Synlett 583 5862007 -, , 4 ,

Sonogashira Reaction.Pd

Spectral properties (fluorescence).

REDDY, M. R.; SHIBATA, N.; YOSHIYAMA, H.; NAKAMURA, S.; TORU, T.

MJ

Zn

= phthalocyanine

I I

I I

Zn+ R

R = O

TolO

TolO

RR

R R75%

PdCl2(PPh3)2 (cat.)CuI (cat.)

NEt3, DMFrt, 72 h

Zn

Synlett 628 6322007 -, , 4 ,

45

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Carbonylative Cyclization.Pd

The products ratio depends on R and L. Chiral ligands have also been used (up to 95% ee).

KATO, K.; TERAGUCHI, R.; YAMAMURA, S.; MOCHIDA, T.; AKITA, H.; PEGANOVA, T. A.; VOLOGDIN, N. V.;GUSEV, O. V.

MJ

O

O

R

O

O

O

O

MeO

MeO

R

MeO2C

OMe

Pd(OCOCF3)2 (0.05 eq.)L (0.75 eq.)

p-benzoquinone (2 eq.)

CO (balloon)MeOH

+

R

up to 79%

Synlett 638 6422007 -, , 4 ,

Chiral Catalysts.Pd

Kinetic resolution of alcohols using these complexes.

NGUYEN, H. V.; MOTEVALLI, M.; RICHARDS, C. J.

MJ

N

Br

N PdCl2, P(t-Bu)3CsF, CuI

Fe

FeDMF, ∆

SnBu3

N

N

82%

+Co

N

N

14%

Othersynthesis:

Ph

PhPh

PhBr

Fe

FeCoZnSn

Synlett 725 7282007 -, , 5 ,

Cyclization.Pd

The reverse order of these 2 steps led to a lower yield.

DEUTSCH, C.; HOFFMANN-RÖDER, A.; DOMKE, A.; KRAUSE, N.

MJ

HO OTBS

H

Br

AuCl3 (0.01 eq.)

THF

72%

Br

O

OTBS

O

OTBS

Me3Si

SiMe3PdCl2(PPh3)2 (0.02 eq.)

CuI (0.04 eq.)

NEt392%

AuCu

Synlett 737 7402007 -, , 5 ,

Cross-Coupling.Pd

Lower yields with Pd(0) catalysts. 18 examples.

ENDO, M.; SAKURAI, T.; OJIMA, S.; KATAYAMA, T.; UNNO, M.; MATSUMOTO, H.; KOWASE, S.; SANO, H.; KOSUGI, M.;FUGAMI, K.

MJ

O

SiO

Si

OSi

Ar

Ar

ArAr

Ar

ArBr OMe+

Pd(OAc)2 (0.05 eq.)

KOH (10 eq.)

(ca. 0.2 eq.)

dioxane/H2O (1:1)reflux, 4 h

Ar = Ph: 87%

Ar OMe

Si

Synlett 749 7522007 -, , 5 ,

46

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

New Chelating Ligand. Heck Reaction.Pd

13 examples.

PATHAK, D. D.; MAHESWARAN, H.; PRASANTH, K. L.; KANTAM, M. L.

MJ

R

Ar

R

ArX +

R = Ar', COOMe, CNX = Br, I: 69-89%X = Cl: 20%

Cat. (0.05 eq.)n-Bu3N (1.2 eq.)

(1.2 eq.)DMF, 85-130 °C

Cat.:

N NH

O

PPd

O

P

Cl Cl

Synlett 757 7602007 -, , 5 ,

An Alternative Reagent fo Pd-Catalyzed Borylation of Aryl Halides Pd

MURATA, M.; ODA, T.; WATANABE, S.; MASUDA, Y.

PG

BH3.Me2S + OHHO

B

O

OH

CH2Cl20°C to rt

78 %

ArILigand

PdCl2(MeCN)2Et3N

PhCH380°C

B

O

O

Ar

9 examples72-93%

B

Synthesis 351 3542007 -, , 3 ,

High T.O.N. in Suzuki Cross-Coupling with a Phosphine Free Pd-CatalystPd

CUI, X.; QIN, T.; WAY, J.-R.; LIU, L.; GUO, Q.-X

PG

X

R

B(OH)2+

R

Pd(OCOCH2NMe2)K3PO4

50°C, air, 1hEtOH/H2O

X = Br, I 23 examples88-99%TON 104

R'

R'

B

Synthesis 393 3992007 -, , 3 ,

Pd-Catalyzed Synthesis of 5H-Imidazo[2,1-a]isoindolesPd

DE FIGUEIREDO, R. M.; THORET, S.; HUET, C.; DUBOIS, J.

PG

DMFµW, 15 min

N

NI

R'

R N

N

R

R

Pd(OAc)2 (10 mol%)P(o-Tolyl) (30 mol%)

AcOK 16 examples18-72%

Synthesis 529 5402007 -, , 4 ,

47

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Easy Access to γγγγ-Alkylidenebutenolide and Phthalide SkeletonsPd

DUCHENE, A.; THIBONNET, J.; PARRAIN, J.-L; ANSELMI, E.; ABARABRI, M.

PG

SnBu3

I

O

OSnBu3+

Pd(PPh3)4

DMFO

O

Bu3Sn

RXPdCl2(MeCN)2

O

O

R6 examples

65-75%10 examples

58-77%

Synthesis 597 6072007 -, , 4 ,

Microwave Assisted Heck Reaction in WaterPd

ZHU, M.; SONG, Y.; CAO, Y.

PG

WaterµW, 20 s

CO2H + Ar2I ClPdCl2 (1 mol%)

CO2HAr 9 examples

78-85 %

Synthesis 853 8562007 -, , 6 ,

Pd-Catalyzed Cross-Coupling Chiral BenzylsulfanyloxazolinesPd

LECONTE, N.; PELLEGATTI, L.; TATIBOUËT, A.; SUZENET, F.; ROLLIN, P.; GUILLAUMET, G.

PG

O

NSBn

RB(OH)2or

RSnBu3+

[Pd(0)]

O

NR

13 examples55-93%* *

BSn

Synthesis 857 8642007 -, , 6 ,

Palladium-Catalyzed Synthesis of 3,3-Disubstituted -2,3-Dihydrobenzofuran.Pd

SZLOSEK-PINAUD, M.; DIAZ, P.; MARTINEZ, J.; LAMATY, F

AM

OH

IBr

CO2MeO

I

+ CO2Me

O

CO2MeNu

base Pd cat./ Nu

one pot versionNu , Pd cat., base

20 examples

Tetrahedron 3340 33492007 63 -, , 16 ,

48

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Palladium-Catalyzed Amination and/or Nucleophylic Aromatic Substitution.Pd

Examination of the mecanism of the title intramolecular reaction is described.

LOONES, K. T. J.; MAES, B. U. W.; HERREBOUT, W. A.; DOMISSE, R. A.; LEMIERE, G. L. F.; VANDER VEKEN, B. J.

AM

X

NH

N

N

NPd - catalystor

base assistedSNAr

X = Br, Cl

Tetrahedron 3818 38252007 63 -, , 18 ,

Mecanistic Aspects in the Palladium-Catalyzed Reduction of Alkenes.Pd

BRUNEL, J. M.

AM

R4

R1 R2

R3 R4

R1 R2

R3yields varying from 25 to 98%

2 mol % Pd(OAc)24 mol % P(t-Bu)4

HCO2 (5 eq.)THF, reflux to r.t

Tetrahedron 3899 39062007 63 -, , 18 ,

Hydroxyl Group Deprotection Reactions with Pd(OH)2 / C.Pd

A convenient alternative to hydrogenolysis of benzyl ethers and acid hydrolysis of ketals is reported.

MURAL, C.; SHASHIDAR, M. S.; GOPINATH, C. S.

AM

O

O

R2R1

R-O-CH2Phor

Pd(OH)2 / C

MeOHOH

OH

ROH

or

Tetrahedron 4149 41552007 63 -, , 19 ,

Palladium-Catalyzed Allylic Alkylation of Secondary Nitrones.Pd

MAKI, K.; KANAI, M.; SHIBASAKI, M.

AM

R1 OBocR2

R3 R4NO2

R5R1

R2

R3R4

R5NO2

Pd cat. (1-2%)PPh3 or rac-BINAP or iPr-PHOX (6 mol%)

+DBU (10 mol%)DMSO, r.t to 50°C

R1 = Ph, R2 = R3 = H: up to 94% ee70-100% yield

NO

iPr

iPr-PHOX :

Tetrahedron 4250 42572007 63 -, , 20 ,

49

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Palladium-Catalyzed Dehalogenation of Aryl Halides and αααα-Haloketones.Pd

CHEN J.; ZHANG, Y.; YANG, L.; ZHANG, X.; LIU, J.; LI, L.; ZHANG, H.

AM

XR

HR R' Br

O

R' HO

1-5 % Pd(OAc)24-20 % PPh3

alcohol, K2CO3100°C, 87-98%

alcohol, K2CO3100°C, 90-98%

1% Pd(OAc)24% PPh3

R = functional group; R' = Ar, Alkyl; X = Cl, Br, I

Tetrahedron 4266 42702007 63 -, , 20 ,

Asymmetric Allylic Alkylation using N-heterocyclic Carbene–Amino LigandsPd

FLAHAUT, A.; ROLAND, S.; MANGENEY, P.

CS

Ph

OAc

Ph

Pd[allyl)Cl]2, 3 mol%NHC-AgCl, 8.5 mol%

dimethyl malonate / NaH Ph Ph

CO2MeMeO2C

80% ee

N N

HNPh

PhEt

AgCl

i-Pr

NHC-AgCl =

Tetrahedron Asymm. 229 2362007 18 -, , 2 ,

Synthesis of Planar Chiral [2.2]paracyclophane Monophosphine Ligands Pd

ZHANG, T.-Z.; DAI L.-X.; HOU, X.-L.

CS

RCHO +

OAc [η3-(C3H5PdCl)2]

ligand 8

Et2Zn, THF

R

OH

d.r. up to 99:1ee up to 72%

PR2

(S)-8a-9

Zn

Tetrahedron Asymm. 251 2592007 18 -, , 2 ,

Microwave Assisted Asymmetric Suzuki-Miyaura and Negishi Cross-coupling ReactionsPd

GENOV, M.; ALMORýN A.; ESPINET, P.

CS

BrR

B(OH)2R

Zn 2R'

R'R[Pd]/L*, MW, 60 min. [Pd]/L*, MW, 45 min.

up to 70% eeR, R' = H, Me, OBn, OMe

R'R

up to 70% eeR, R' = H, Me, OBn, OMe

Tetrahedron Asymm. 625 6272007 18 -, , 5 ,

50

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Pd-Catalyzed Reaction of 1,3-Diketones with MethyleneaziridinesPd

KATHRIARACHCHI, K.K.; SIRIWARDANA, A.I.; NAKAMURA, I.; YAM AMOTO, Y.

TJ

N

R1 O

R2 R2

O+

N

O

R2

R2

R1

Pd(PPh3)4 25 mol%

benzene, 120 °C3 d

9 examples49-90%

R1 = Bn, p-MeC6H4CH2, n-HexR2 = Me, Et, -(CH2)n-

Tetrahedron Lett. 2267 22702007 48 -, , 13 ,

Pd-Catalyzed Reductive Heck CyclizationsPd

LIU, P.; HUANG, L.; LU, Y.; DILMEGHANI, M.; BAUM, J.; XIANG, T.; ADAMS, J.; TASKER, A.; LARSEN, R.; FAUL, M.M.

TJ

R1

R2

X

YZ

R3

R1

R2 YZ

R3Me

n

n 18 examples70-99%

n = 0,1X = Cl, Br

Y = NBoc, NAc, O; Z = CH2Y = CH2; Z = NBoc, O

Pd-Cat,

Base/HCO2NaDMF, 85-95 °C

Tetrahedron Lett. 2307 23102007 48 -, , 13 ,

Direct Pd-Catalyzed C-3 Arylation of IndolesPd

ZHANG, Z.; HU, Z.; YU, Z.; LEI, P.; CHI, H.; WANG, Y.; HE, R.

TJ

NH

R1

NH

R1

R2

+Br

R2Pd-Cat 5 mol%

K2CO3dioxane, reflux

Pd PP OHHO

Pd Cat. =

6 examples12-80%

Tetrahedron Lett. 2415 24192007 48 -, , 13 ,

Suzuki-Miyaura CouplingPd

A mechanistic rationale for these unusual observations is suggested.

MCMILLAN, F.M.; MCNAB, H.; REED, D.

TJ

N Br

(HO)2BCHO

+

N CO2H

N

Pd(PPh3)4 3mol%

MeO(CH2)2OMeNa2CO3/H2O20 h, reflux 94%

Tetrahedron Lett. 2401 24032007 48 -, , 13 ,

51

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

PMHS as a Protectant in Pd-Catalyzed Cyanation ReactionPd

MARTIN, M.T.; LIU, B.; COOLEY, B.E.; EADDY, J.F.

TJ

Br CN

Zn(CN)2Pd(OAc)2 0.9 mol%DPPF 0.12 mol%

NMP/H2O1 wt % PMHSR R

8 examples61-97%

R = CF3, OMe, COMe, NHAc

Zn

Tetrahedron Lett. 2555 25572007 48 -, , 14 ,

Selective Pd-Catalyzed AminationPd

BAEZA, A.; BURGOS, C.; ALVAREZ-BUILLA, J.; VAQUERO, J.J.

TJ

NN

N

X

Cl

Br

NN

N

X

Cl

NN H RRR

R

NaOtBuPd(OAc)2

phosphine, THF

19 examples31-90%

X = H, Cl

Tetrahedron Lett. 2597 26012007 48 -, , 14 ,

Cross-Coupling Reactions of Triarylbismuths with Aryl BromidesPd

RAO, M.L.N.; BANERJEE, D.; JADHAV, D.N.

TJ

Br3R1

+

R2

Bi

3R1

R2

Pd(OAc)2 0.1 equivPPh3 0.4 equiv

K3PO4 6 equivDMF, 90 °C, 1-2 h

25 examples49-95%

Bi

Tetrahedron Lett. 2707 27002007 48 -, , 15 ,

Pd-Catalyzed Amination of Electron-Rich IndolePd

SCHWARZ, N.; TILLACK, A.; ALEX, K.; SAYYED, I.A.; JACKSTELL, R.; BELLER, M.

TJ

N

OTBS

Me

Me

Br+ NH

R1

R2

Pd(OAc)2 1 mol%Ligand 2 mol%

LiHMDS, toluene100 °C, 24 h N

OTBS

Me

Me

NR1

R2 N

Ligand =

Padamantane

adamantane

10 examples40-91%

Tetrahedron Lett. 2897 29002007 48 -, , 16 ,

52

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

Preparation of S-Aryl ThioacetatesPd

LAI, C.; BACKES, B.J.

TJ

X

R

X = Br, OTf

S

RO

Me

O

Me S-K+

Pd2(dba)3Xantphos 5 mol%

iPr2NEtdioxane, MW

160 °C, 25 mn

8 examples51-91%

Tetrahedron Lett. 3033 30372007 48 -, , 17 ,

Access to Funtionalized Indoles by Cycloisomerization of 2-Propargyl AnilinesPt

The same reaction also occurs with Au(III) catalysts

CARIOU, K.; RONAN, B.; MIGNANI, S.; FENSTERBANK, L.; MALACRIA, M.

CY

OAc

N NN

PtCl2 (5 mol%),toluene, temp.

+

temp. = room temp. : 94% : 0%temp. = 110 ° C: 0% : 60%

OAcOAc

Au

Angew. Chem. Int. Ed. 1881 18842007 46 -, , 11 ,

Furan Derivatives from Rearrangement of Allenyl SulfidesPt

Depending on the substrate, the reaction is better performed with Pt, Ru or Rh based catalyst

PENG, L.; ZHANG, X.; MA, M.; WANG, J.

CY

O

PhSPh

C

MeO

H

O

Ph H

MeOSPh

PtCl2 (5 mol%) or{RuCl2(p-cymene)}2 (5 mol%)

toluene, 80 °C

73% with Pt cat.93% with Ru cat.

RuRh

Angew. Chem. Int. Ed. 1905 19082007 46 -, , 11 ,

Synthesis of Spirocyclic 3(2H)-Furanones and 3-PyrrolonesPt

BINDER, J. T.; BENEDIKT CRONE, B.; KIRSCH, S. F.; LIÉBERT, C.; MENZ, H.

BJL

OOH

R1

PtCl2 or AuCl3 catO

R1

11-93%

N

O

R1R2

R2NH2

PtCl2 cat

33-81%

Au

Eur. J. Org. Chem. 1636 16472007 -, , 10 ,

53

Bibliographic Notebooks For Organometallic Chemistry 2007, 25, ( 3)

On Accounting for the Stereoselective Control of the Rautenstrauch ReactionPt

Computational study

SOIRANO, E.; MARCO-CONTELLES, J.

MV

OCOR

PtCl2

OCOR

OCOR

J. Org. Chem. 2651 26542007 72 -, , 7 ,

Cyclization/1,2-Migration for the Synthesis o