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Cyclopentadienyl-Ruthenium Catalysts--- One Group of Ru(II) Complexes

Huijun ZHANG

2007-07-13

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Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

3

Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

4

Ruthenium Complexes

“Ruthenium complexes have a variety of useful characteristics including high electron transfer ability, high Lewis acidity, low

redox potentials, and stabilities of reactive metallic species such as oxometals, metallacycles, and metal carbene complexes."

Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.

Electron configuration: (Kr)4d75s1 Oxidation states: 2,3,4,6,8

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Ruthenium Complexes

Naota, T.; Takaya, H.; Murahashi, S.-I. Chem. Rev. 1998, 98, 2599.

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Cyclopentadienyl-Ruthenium Complexes

Trost, B. M.; Frederiksen, M. U.; Rudd, M. T. Angew. Chem., Int. Ed. Engl. 2005, 44, 6630

Ruthenium-Catalyzed Reactions—A Treasure Trove of Atom-Economic Transformations

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Cyclopentadienyl-Ruthenium ComplexesCp- and Cp*-Ru(II) Complexes:

Relationship between Structures and Reactivities:

Dérien, S.; Dixneuf, P. H. J. Organomet. Chem. 2004, 689, 1382Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178

Ru

Cl

RR

R R

R

Ru

NCMeMeCNMeCN

[PF6]RR

R R

R

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Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

9

Key Features of Cp Ligands

• The M-Cp bond dissociation is large (ferrocene is stable to 400 oC).

• The ligand blocks several coordination sites.

• The ligand tends not to get involved chemically (although it certainly can from time to time).

• It has excellent NMR properties.

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C5H4R

PetroleumIndustry

+rt.

~150oC

R

H

Unmethylated Cyclopentadienes

Okuda, J. Top. Curr. Chem. 1992, 160, 97.Halterman, R. L. Chem. Rev. 1992, 92, 965.

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C5HMe4R

H

Li2

RCOOEtR OH

H+

-H2O H

R

R=Me, Et, nPr, nBu and Ph J. Organomet. Chem. 1977, 136, 1. Org. Synth. 1987, 65, 42. R=iPr J. Organomet. Chem. 1998, 559, 181.R=CF3 J. Am. Chem. Soc. 1992, 114, 6942.

R: containing terminal functional groups Synthesis 1993, 684.

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C5HMe4R

R=Me J. Organomet. Chem. 1983, 243, 119. Organometallics 1988, 7, 1828. Inorg. Synth. 1992, 29, 193. . R=CH2CH2CH=CH2 J. Organomet. Chem. 1988, 344, C1-C4.

R=tBu J. Organomet. Chem. 1996, 520, 265.

O 2 MeCHO

O

O

H+

-H2O O1) RLi

2) H+, -H2O H

R

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C5H2R1R2R3CO2Et

CO2Et

R1 PPh3BrNaHCO3

CO2Et

R1 PPh3

EtO2C

R1 PPh3

R2

O

X

R3 R3

R2EtO2C

R1

Hatanaka, M; Himeda, Y.; Ueda, I. J. Chem. Soc., Chem. Commun. 1990, 526.

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C5HR4R’

Xi, Z.; Li, P. Angew. Chem., Int. Ed. Engl. 2000, 39, 2950.

R: Me, Et, n-Pr, n-Bu, Ph···R’CHO: aliphatic or aromatic aldehyde

Cp2ZrCl22 n-BuLiToluene

-78oC, 1h

Cp2ZrBu22 R R

rt, 1h

ZrCp2

RR

RR

R'CHO/AlCl3

[ClAlO]

RR

RR

R'H

regioisomers about the double bonds

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Recent Two Examples

Funami, H.; Kusama, H.; Iwasawa, N. Angew. Chem. Int. Ed. 2007, 46, 909. Lee, J. H.; Toste, F. D. Angew. Chem. Int. Ed. 2007, 46, 912.

PtCl2( 0.05 equiv)4-A M.S., ClCH2CH2Cl, rt.

R1

R4

R3

R2R2

R3

R4

R1

or Ph3PAuCl(2.0mol%), AgSbF6(2.0mol%)CH2Cl2, 0oC

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Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

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[Ru(η5-C5R5)(MeCN)3]+ Complexes

"RuCl3 3H2O"

+ C5HMe5

[Ru(C5Me5)Cl2]2

[Ru(C5Me5)Cl]4

Ru

MeCNMeCN

NCMe

[PF6]MeOHreflux

LiBHEt3 THF

Zn, KPF6

MeCN

KPF6MeCN

III

II

Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc. 1989, 111, 1698Steinmetz, B.; Schenk, W. A. Organometallics 1999, 18, 943

Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C. Adv. Synth. Catal. 2004, 346 (7), 835

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[Ru(η5-C5R5)(MeCN)3]+ Complexes

Ru MeCN Ru

MeCNMeCN

NCMe

1) TlCp, rtMeCN

2) NH4PF6Ru

[PF6]

hv.Ru

MeCNMeCN

NCMe[(C6H6)RuCl2]2[(C6H6)RuCl2]2

[PF6]

Ru

MeCNMeCN

NCMe

[PF6]COOEt

Me

R

R= Ph or Me

T. P. Gill, K. R. Mann, Organometallics 1982, 1, 485.Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett. 1996, 677.

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Ru(η5-C5R5)(η4-diene)Cl complexes

Ru

H

Ru

Cl

1/x [Ru(COD)Cl2]x[Ru(H2NNMe2)3(COD)(H)Cl]+

"RuCl3 3H2O"

Ru

Cl

COD = 1,5-cyclooctadiene

CpTl

CCl4

KC9H7

COD

Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.; Bassetti, M. Organometallics 2001, 20, 3762

Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics 1986, 5, 2199

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Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

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Cp-Ru Catalyzed C-C Bond Formation Reactions

• Reactions Involving Ruthenacyclopentanes, Ruthenacyclopentenes, Ruthenacyclopentadienes

• Heteroatom Additions to Alkynes

• Reactions Involving Additions of Diazo Compounds

• Reactions Initiated by Hydrometalations

• Regioselective Allylation of Nuclephiles

• Reactions Initiated by C-H Bond Activation

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Reactions Involving Ruthenacyclopentanes

Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 4068.

Ru

+ R'

O

RuO

R'

RuO

R'

HR

H

+

+

RuH

O

R'

+

R

R

R

R

R'

O

R

O

R'+10% CpRuCl(cod)

15% CeCl3 7H2ODMF, 60oC

RR'

O

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Reactions Involving Ruthenacyclopentane

+ 10% CpRu(CH3CN)3PF6

15% CeCl3 7H2ODMF, 60oC

HO

O

O

O

HO [Ru+ O

2

Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 10842.Trost, B. M.; Pinkerton, A. B.; Kremzow, D. J. Am. Chem. Soc. 2000, 122, 12007.

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Reactions Involving Ruthenacyclopentane

Fujiwhara, M.; Nishikawa, T.; Hori, Y. Org. Lett. 1999, 1, 1635.

+ OAc0.7% Cp*RuCl(cod)

MeOH, 100oC

OAc

[Ru+OAc

H

OAc

96

4

:

[Ru+OAc

H

H

+

+

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Reactions Involving Ruthenacyclopentene

An Alder-Ene Type Reaction:

Trost, B. M.; Indolese, A. J. Am. Chem. Soc. 1993, 115, 4361.Trost, B. M.; Indolese, A. F.; Mu¨ ller, T. J. J.; Treptow, B. J. Am. Chem. Soc. 1995, 117, 615.

H nBu +nBu

nBunBu

nBunBu

B

L

+

B/L= 5.2/1

10% CpRu(COD)Cl

20% NH4PF6MeOH, reflux

R + R'

[Ru [Ru

[Ru+

R'

H

R

R R'R

R'

Branched Linear

[Ru+

R'

HR

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Reactions Involving Ruthenacyclopentene

Trost, B. M.; Müller, T. J. J. J. Am. Chem. Soc. 1994, 116, 4985.

5

MeO2C

OH10% CpRuCl(cod)

MeOH, 60oC

O

OO

O

5

[Ru+

R'

HO

MeO2C

[Ru2+

R'

HO

MeO2C-

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Reactions Involving Ruthenacyclopentene

Trost, B. M.; Martinez, J. A.; Kulaweic, R. J.; Indolese, A. F. J. Am. Chem. Soc. 1993, 115, 10402.

4

MeO2C

10% CpRu(CH3CN)3PF6

DMF, rt

[Ru+

OH

O

CO2Me

4

O

4

CO2Me

2.3

1

:

CO2Me

H

HO

4

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Reactions Involving Ruthenacyclopentene

De´rien, S.; Dixneuf, P. H. J. Chem. Soc. Chem. Commun. 1994, 2551.

R + OH 5% Cp*RuCl(COD)

neat, r.t., 15min

R CHO+R

CHO

major

Ph CHO

85%(75/25)

But CHO MeOH2C CHO

60%(100/-) 70%(76/24)

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Reactions Involving Ruthenacyclopentene

Matsushima, Y.; Kikuchi, H.; Uno, M.; Takahashi, S. Bull. Chem. Soc. Jpn. 1999, 72, 2475. Kikuchi, H.; Uno, M.; Takahashi, S. Chem. Lett. 1997, 1273.

OH

1% Cp'Ru(CH3CN)3PF6

MeOH, rtO

[Ru+HO [Ru+HO

Cp' =

CO2Et

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Reactions Involving Ruthenacyclopentadiene

MeO2C

MeO2C 1% Cp*RuCl(cod)

O, 40oC

MeO2C

MeO2CO

Ru

+

Ru

+

R'

R

Ru

R'

R

+

Ru

+

R'

R

R'

R'

Yamamoto, Y.; Kitahara, H.; Ogawa, R.; Itoh, K J. Org. Chem. 1998, 63, 9610. Yamamato, Y.; Kitahara, H.; Ogawa, R.; Kawaguchi, H.; Tatsumi, K.; Itoh, K.

J. Am. Chem. Soc. 2000, 122, 4310.

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Heteroatom Additions to Alkynes

5% CpRuCl(cod)

NH4PF6, In(OTf)3DMF/H2O 1/1, 100oC

NC(H2C)3

O

+ NC(H2C)3

O O

Additions of Water

Trost, B. M.; Krause, L.; Portnoy, M. J. Am. Chem. Soc. 1997, 119, 11319.

Ru

+

Ru

Ru

+

+

Ru O

R'

+

R

O

R' R

RH2OH+

Ru

+

OH

R

R

OR'

O

Ru

+

R

O R'

O

O

H+

R

O

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Heteroatom Additions to Alkynes

Ru

+

OR'

R

Ru

R

R'O H2O

Ru

R

R'O

HO

Ru

R

R'O

O

H

+ +

+

R'

RO

O

ORu

R'

R+

O

R'

R

Intramollecular Version

OPh

H3CO2C

H3CO2C

10% CpRu(CH3CN)3PF6

CSA, H2Oacetone, rt

5% CpRu(CH3CN)3PF6

acetone, rtO

Ph

O

O

Ph

H3CO2CH3CO2C

H3CO2CH3CO2C

Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am. Chem. Soc. 2000,122, 5877.

33

Heteroatom Additions to Alkynes

Additions of Halides

Ru+ + X- R+

R

Ru+X-R

RuXX Ru

R

O

R

X

O

Z

R Ru

X

O

X

R

O

E

Trost, B. M.; Pinkerton, A. B. J. Am. Chem. Soc. 1999, 121, 1988.

CN

O

10% CpRuCl(cod)

SnCl4,5H2O, N(CH3)4ClDMF, 60oC8.2:1, E:Z

+

CN

Cl

O

34

Heteroatom Additions to Alkynes

Additions of Carboxylic Acids

Cp*RuCl(cod)dioxane, rt+

H3CO

CH3COOH O2CCH3

H3CO

OCH3

Le Paih, J.; Monnier, F.; Dérien, S. J. Am. Chem. Soc., 2003, 125, 11964.

Ru

+

R

CH3CO2H

Ru

RR-O2CCH3

Ru

+

R RRu

+

R

H

H3CCO2

RR

H

2+

R

O2CCH3

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Reactions Involving Additions of Diazo Compounds

Me3Si

SiMe3

OH

N2

SiMe3 5% Cp*RuCl(cod)

dioxane, 60oC+2

OH

Le Paih, J.; Dérien, S.; Özdemir, I.; Dixneuf, P. H. J. Am. Chem.Soc. 2000, 122, 7400.

RuCl

RuClSiMe3

RuClSiMe3

R R'

RuClSiMe3

R R'

RuCl

RSiMe3

R'

SiMe3

N2SiMe3

Me3Si

SiMe3

R'

R

R R'

R R'

N2SiMe3

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Reactions Initiated by Hydrometalations

Le Paih, J.; Rodrı´guez, D. C.; De´rien, S.; Dixneuf, P. H. Synlett 2000, 95.

OPh 5% Cp*RuCl(cod)

EtOD, rtO

Ph

Ru D

O

DPh

Ru O

Ph

Ru

H

D

D

O

RuPh

D

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Regioselective Allylation of Nuclephiles

OCO2Me + HNCp*RuCl(COD)

0oC, THFN

Ph

Ph N+

84 16(overall yield 99%)

B L:

Ph OCO2tBu

+

NaCH(CO2Me)2

1% catalyst

DMF, rt.Ph

MeO2C CO2Me

PhCO2Me

CO2Me

+

B L

[Cp*Ru(NCCH3)3]PF6

[CpRu(NCCH3)3]PF6 1 2

9 1

Trost, B. M.; Fraisse, P. L.; Ball, Z. T.; Angew. Chem. Int. Ed. 2002, 41, 1059.

Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.; Watanabe, Y. Organometallics 1995, 14, 1945.

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Oxidative Addition of Allylic Substrate

Key Step in Ruthenium-Catalysed Allylic Substitution Reactions

Bruneau, C.; Renaud, J-L.; Demerseman, B. Chem. Eur. J. 2006, 12, 5178

RuX

XPh

Ru

X LL

2 L

Ph XNu-

Ph

Nuand

Ph Nu2 L

X-

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Planar Chiral Ruthenium Catalysts

Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S.J. Am. Chem. Soc. 2001, 123, 10405.

Ph Ph

OCO2EtNuNa

Ph Ph

Nu

63% ee 97%

RO

O

PRu

Ar ArMeCN

MeCN

[PF6]

(5 mol%)THF, 20oC, 6h

>

+

>

NuNa= NaCH(CO2Me)2, NaCH(CO2Et)2, NaCMe(CO2Me)2R= Me, Ph, tBu; Ar= Ph, o-MeC6H4, 3,5-Me2C6H3

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Reactions Initiated by C-H Bond Activation

TBDMSOCOOEt 10% CpRu(CH3CN)3PF6

DMF, rt

COOEtTBDMSO

Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728.

Ru

+

Ru

+

+

COOEt

COOEt

Ru

+

COOEtH

EtOOC

RuH

EtOOCTBDMSO

TBDMSO

TBDMSO

TBDMSO

TBDMSO

Ru

TBDMSOCOOEt

+

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Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook

42

Outlook

• New sterically demanding catalysts with bulky, electron rich C5R5 ligands

• New optically active catalysts with chiral C5R4R* ligands

• Polymerizable catalysts for the recovery and recycling of catalysts.

R

R

RR

R[Ru

[Ru: RuCl(COD), Ru(NCMe)3+, RuHL2

R

R

R

R[Ru

R3

R1

R2*

[Ru

R

RR

R

n

etc.

“Teaching An Old Dog New Tricks”

43

Acknowledgement

Laboratoire de Catalyse et Organométalliques

Prof. Zhenfeng Xi, Prof. Zhiping LiProf. Pierre Dixneuf, Dr. Christian Bruneau,

Dr. Bernard Demerseman

All Professors in the Institute of Organic Chemistry

All my lab mates

Peking U. Team: Rennes U. Team:

44

Thank you for your attention!

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Proposed Mechanism

ZrCp2

R

HO L.A.

path a

path b

Cp2ZrCl2

L.A.

R

H

O

ZrCp2

R

O

ZrCp2

O

RL.A.

Cp2Zr=O

L.A.

R

H

OL.A.

R[ClAl=O]n

R

H

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Ruthenium Hydride

RuIIClLn

¦Â-H elimination-CH3CHO

-H+

- ClRuIILn

+ CH3CH2OH H3CHC OH

H RuIILn

+

H

RuIILn