1. Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet
Phillips Triolefin Process (1964) with Mo(CO)6 AlO2, WO3 SiO2
Nobel Prize in 2005

2. Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet
Overview of the available catalysts
167 CHF/g
3505
582 CHF/g
3279
Price on Sigma-Aldrich
Number of ref on SciFinder
3500 CHF/g
315
612 CHF/g
343
392 CHF/g
1392
For Mo-Schrock: Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875–3886.
For G-I : Schwab, P.; France, M.B.; Ziller, J.W.; Grubbs, R.H. Angew. Chem. Int. Ed. 1995, 34,
For G-II : Scholl, M.; Trnka, T.M.; Morgan, J.P.; Grubbs, R.H., Tetrahedron Lett. 1999, 40,
For GH-I: Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791–799.
For GH-II: Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168–8179.

3. < = Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet
Molybdenum-based
catalysts
Ruthenium-based
catalysts
Schrock vs Grubbs
ACTIVITY
STABILITY
Efficient for very hindered olefin
Broad tolerance
Alkyne metathesis
Non tolerant to oxo functionnal groups
(carbonyl, hydroxyl, etc)
Non tolerant to phosphine, sulfure or electron-rich amine groups
< =
“They are the two wings of the same angel.
The angel can't fly if you clip either one.” Amir Hoveyda

4. Phosphine-free ligands
Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet
Phosphine ligands
NHC ligands
1st gener. vs 2nd gener.
Similar group tolerance and thermal stability
Better catalytic activity
Phosphine ligands
Phosphine-free ligands -
Faster kinetic
Grubbs vs Hoveyda
Trouble with sulfure group -

5. Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet
The new modified catalysts
Grubbs III
(G-III)
Piers II
(P-II)
605 CHF/g 24
555 CHF/g
456
690 CHF/g 96
nitro-Grela
2924 CHF/g
456
Stewart-Grubbs
New battle in perspective with ruthenium catalysts?
Mo-catalyst in paraffin pellets
For G-III : Sanford, M. S.; Love, J. A.; Grubbs, R. H. Organometallics 2001, 20, 5314–5318.
For Piers: Romero, P. E.; Piers, W. E.; McDonald, R. Angew. Chem. Int. Ed. 2004, 43,
For Stewart-Grubbs: Stewart, I. C.; Douglas, C. J.; Grubbs, R. H. Org. Lett. 2008, 10,
For nitro-Grela: Angew. Chem. Int. Ed. 2002, 41,
For Schrock paraffin pellets: Nguyen, T. T., Koh, M. J.; Shen, X.; Romiti, F.; Schrock, R. R.; Hoveyda, A. H. Science 2016, 352,

6. nitro-Grela Piers II (P-II) Stewart-Grubbs Schrock HG-I HG-II Grela
167 CHF/g
3505
582 CHF/g
3279
612 CHF/g
343
392 CHF/g
1392
3500 CHF/g
315
555 CHF/g
456
nitro-Grela
2924 CHF/g
160
Piers II
(P-II)
605 CHF/g 24
Stewart-Grubbs
690 CHF/g 96
Price on Sigma-Aldrich
Number of ref on SciFinder
For Mo-Schrock: Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875–3886.
For G-I : Schwab, P.; France, M.B.; Ziller, J.W.; Grubbs, R.H. Angew. Chem. Int. Ed. 1995, 34,
For G-II : Scholl, M.; Trnka, T.M.; Morgan, J.P.; Grubbs, R.H., Tetrahedron Lett. 1999, 40,
For HG-I: Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791–799.
For HG-II: Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168–8179.
For G-III : Sanford, M. S.; Love, J. A.; Grubbs, R. H. Organometallics 2001, 20, 5314–5318.
For nitro-Grela: Angew. Chem. Int. Ed. 2002, 41,
For Piers: Romero, P. E.; Piers, W. E.; McDonald, R. Angew. Chem. Int. Ed. 2004, 43,
For Stewart-Grubbs: Stewart, I. C.; Douglas, C. J.; Grubbs, R. H. Org. Lett. 2008, 10,
1990
1995
1999
2000
2001
2002
2004
2008
Schrock
HG-I
HG-II
Grela
S-G
G-I
G-II
G-III
P-II