Olefin Metathesis

Richard Schrock, MIT, Robert Grubbs, Caltech, Yves Chauvin, France: 2005
Chemistry Nobel Prize
 What is Olefin Metathesis?

Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.

Ring Closing Metathesis
Ring Opening Metathesis
Metathesis in Chemistry

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 Metals in Metathesis

Ti V Cr

Nb Mo Ru

Ta W Re Os Ir Pt

Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18. 6

 2005 Nobel Prize for Metathesis

Chauvin, Y.; Schrock, R. R.; Grubbs, R. H. Angew. Chem. Int. Ed. 2006, 47, 3740. 7
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Grubbs catalyst
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 Metathesis in Synthesis

Alzheimer's diseases

Ciluprevir
Hepatitis C

Hirama, M.; Oishi, T.; Uehara, H.; Inoue, M.; Maruyama, M.; Oguri, H.; Satake, M. Science 2001, 294, 1904.
Martin, S. F.; Humphrey, J. M.; Ali, A.; Hillier, M. C. J. Am. Chem. Soc. 1999,121, 866.
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Faucher, A.-M. Org. Lett. 2004, 6, 2901.
The Catalytic Cycle

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 Mechanism of Olefin Coordination

Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887. 11
 Phosphine Dissociation Experiments

Phosphine exchange monitored by 31P NMR experiments over a range of temperatures

Catalyst will not carry out subsequent metathesis steps

Intermediates are observable by NMR

Key intermediates could not be observed by NMR

Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 749. 12
 Phosphine Dissociation Experiments

Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 749. 13
 Determining Dependence on
Phosphine

2.5

Rate shows no dependence on phosphine concentration

Vary equivalents
2
of phosphine

1.5
k (s-1)
1

0.5

0
0 5 10 15 20 25
PR3 (eq)
Sanford, M. S.; Ulman, M.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 749. 14
 The Grubbs Catalysts

Sholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953. 15
 N-Heterocyclic Carbene Ligands

Gives electron density

Removes electron density

Diez-Gonzalez, S.; Nolan, S. P. Coord. Chem. Rev. 2006, 251, 874.

Straub, B. F. Adv. Synth. Catal. 2007, 349, 204. 16
 The Trans Effect and Ligand Dissociation

Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; VCH: New York, 1997, p 51. 17
 The Trans Effect and Ligand Dissociation

Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; VCH: New York, 1997, p 51. 18
 The Trans Effect and Ligand
Dissociation

Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; VCH: New York, 1997, p 51. 19