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Cyclopentadienyl-Ruthenium Catalysts --- One Group of Ru(II) Complexes. Huijun ZHANG 2007-07-13. Content. Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook. Content. Introduction Cyclopentadienes Cyclopentadienyl-Ruthenium Their Applications Outlook.

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Cyclopentadienyl ruthenium catalysts one group of ru ii complexes l.jpg

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

Huijun ZHANG

2007-07-13


Content l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Content3 l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Ruthenium complexes l.jpg
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."

Electron configuration: (Kr)4d75s1

Oxidation states: 2,3,4,6,8

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


Ruthenium complexes5 l.jpg
Ruthenium Complexes

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


Cyclopentadienyl ruthenium complexes l.jpg
Cyclopentadienyl-Ruthenium Complexes

Ruthenium-Catalyzed Reactions

—A Treasure Trove of Atom-Economic Transformations

Trost, B. M.; Frederiksen, M. U.; Rudd, M. T.

Angew. Chem., Int. Ed.Engl. 2005,44,6630


Cyclopentadienyl ruthenium complexes7 l.jpg
Cyclopentadienyl-Ruthenium Complexes

Cp- and Cp*-Ru(II) Complexes:

Relationship between Structures and Reactivities:

Dérien, S.; Dixneuf, P. H. J. Organomet. Chem.2004, 689, 1382

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


Content8 l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Key features of cp ligands l.jpg
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.


C 5 h 4 r l.jpg
C5H4R

Okuda, J. Top. Curr. Chem. 1992, 160, 97.

Halterman, R. L. Chem. Rev. 1992, 92, 965.


C 5 hme 4 r l.jpg
C5HMe4R

R=Me, Et, nPr, nBu and PhJ. Organomet. Chem.1977, 136, 1.

Org. Synth.1987, 65, 42.

R=iPr J. Organomet. Chem.1998, 559, 181.

R=CF3J. Am. Chem. Soc.1992, 114, 6942.

R: containing terminal functional groupsSynthesis1993, 684.


C 5 hme 4 r12 l.jpg
C5HMe4R

R=Me J. Organomet. Chem.1983, 243, 119.

Organometallics1988, 7, 1828.

Inorg. Synth.1992, 29, 193. .

R=CH2CH2CH=CH2J. Organomet. Chem.1988, 344, C1-C4.

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


C 5 h 2 r 1 r 2 r 3 co 2 et l.jpg
C5H2R1R2R3CO2Et

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


C 5 hr 4 r l.jpg
C5HR4R’

R: Me, Et, n-Pr, n-Bu, Ph···

R’CHO: aliphatic or aromatic aldehyde

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


Recent two examples l.jpg
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.


Content16 l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Ru 5 c 5 r 5 mecn 3 complexes l.jpg
[Ru(η5-C5R5)(MeCN)3]+ Complexes

Fagan, P. J.; Ward, M. D.; Calabrese, J. C. J. Am. Chem. Soc.1989, 111, 1698

Steinmetz, B.; Schenk, W. A. Organometallics1999, 18, 943

Mbaye, M. D.; Demerseman, B.; Renaud, J.-L.; Toupet, L.; Bruneau, C.

Adv. Synth. Catal.2004, 346 (7), 835


Ru 5 c 5 r 5 mecn 3 complexes18 l.jpg
[Ru(η5-C5R5)(MeCN)3]+ Complexes

T. P. Gill, K. R. Mann, Organometallics1982, 1, 485.

Komatsuzaki, N.; Uno, M.; Kikuchi, H.; Takahashi, S. Chem. Lett.1996, 677.


Ru 5 c 5 r 5 4 diene cl complexes l.jpg
Ru(η5-C5R5)(η4-diene)Cl complexes

Alvarez, P.; Gimeno, J.; Lastra, E.; Garcia-Granda, S.; Van der Maelen, J. F.;

Bassetti, M. Organometallics2001, 20, 3762

Albers, M. O.; Robinson, D. J.; Shaver, A.; Singleton, E. Organometallics1986, 5, 2199


Content20 l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Cp ru catalyzed c c bond formation reactions l.jpg
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


Reactions involving ruthenacyclopentanes l.jpg
Reactions Involving Ruthenacyclopentanes

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


Reactions involving ruthenacyclopentane l.jpg
Reactions Involving Ruthenacyclopentane

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.


Reactions involving ruthenacyclopentane24 l.jpg
Reactions Involving Ruthenacyclopentane

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


Reactions involving ruthenacyclopentene l.jpg
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.


Reactions involving ruthenacyclopentene26 l.jpg
Reactions Involving Ruthenacyclopentene

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


Reactions involving ruthenacyclopentene27 l.jpg
Reactions Involving Ruthenacyclopentene

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


Reactions involving ruthenacyclopentene28 l.jpg
Reactions Involving Ruthenacyclopentene

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


Reactions involving ruthenacyclopentene29 l.jpg
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.


Reactions involving ruthenacyclopentadiene l.jpg
Reactions Involving Ruthenacyclopentadiene

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.


Heteroatom additions to alkynes l.jpg
Heteroatom Additions to Alkynes

Additions of Water

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


Heteroatom additions to alkynes32 l.jpg
Heteroatom Additions to Alkynes

Intramollecular Version

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


Heteroatom additions to alkynes33 l.jpg
Heteroatom Additions to Alkynes

Additions of Halides

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


Heteroatom additions to alkynes34 l.jpg
Heteroatom Additions to Alkynes

Additions of Carboxylic Acids

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


Reactions involving additions of diazo compounds l.jpg
Reactions Involving Additions of Diazo Compounds

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


Reactions initiated by hydrometalations l.jpg
Reactions Initiated by Hydrometalations

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


Regioselective allylation of nuclephiles l.jpg
Regioselective Allylation of Nuclephiles

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

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


Oxidative addition of allylic substrate l.jpg
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


Planar chiral ruthenium catalysts l.jpg
Planar Chiral Ruthenium Catalysts

Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S.

J. Am. Chem. Soc. 2001, 123, 10405.


Reactions initiated by c h bond activation l.jpg
Reactions Initiated by C-H Bond Activation

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


Content41 l.jpg
Content

Introduction

Cyclopentadienes

Cyclopentadienyl-Ruthenium

Their Applications

Outlook


Outlook l.jpg
Outlook

“Teaching An Old Dog New Tricks”

  • 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.


Acknowledgement l.jpg
Acknowledgement

Prof. Zhenfeng Xi, Prof. Zhiping Li

Prof. 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:

Laboratoire de Catalyse

et Organométalliques