and Cross Metathesis Erwann Grenet Phillips Triolefin Process 1964 with MoCO6 AlO2 WO3 SiO2 Nobel Prize in 2005 For Mo Schrock Schrock R R Murdzek ID: 1042928
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1. Ring-Closing Metathesis and Cross Metathesis – Erwann GrenetPhillips Triolefin Process (1964) with Mo(CO)6 AlO2, WO3 SiO2Nobel Prize in 2005
2. 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, 2039-2041.For G-II : Scholl, M.; Trnka, T.M.; Morgan, J.P.; Grubbs, R.H., Tetrahedron Lett. 1999, 40, 2247-2250.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.Ring-Closing Metathesis and Cross Metathesis – Erwann GrenetOverview of the available catalysts167 CHF/g3505612 CHF/g343582 CHF/g3279392 CHF/g1392Price on Sigma-AldrichNumber of ref on SciFinder3500 CHF/g315
3. =<Ring-Closing Metathesis and Cross Metathesis – Erwann GrenetSchrock vs GrubbsEfficient for very hindered olefinSTABILITYNon tolerant to oxo functionnal groups(carbonyl, hydroxyl, etc)Molybdenum-basedcatalystsRuthenium-basedcatalystsACTIVITYAlkyne metathesisBroad toleranceNon 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. Ring-Closing Metathesis and Cross Metathesis – Erwann Grenet1st gener. vs 2nd gener.Grubbs vs HoveydaPhosphine ligandsNHC ligandsSimilar group tolerance and thermal stabilityBetter catalytic activityPhosphine ligandsPhosphine-free ligandsFaster kinetic-Trouble with sulfure group-
5. Ring-Closing Metathesis and Cross Metathesis – Erwann GrenetThe new modified catalystsFor 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, 6161-6165.For Stewart-Grubbs: Stewart, I. C.; Douglas, C. J.; Grubbs, R. H. Org. Lett. 2008, 10, 441-444.For nitro-Grela: Angew. Chem. Int. Ed. 2002, 41, 4038-4040.For Schrock paraffin pellets: Nguyen, T. T., Koh, M. J.; Shen, X.; Romiti, F.; Schrock, R. R.; Hoveyda, A. H. Science 2016, 352, 569-574.Stewart-Grubbs2924 CHF/g456Piers II(P-II)605 CHF/g24nitro-Grela690 CHF/g96Mo-catalyst in paraffin pelletsNew battle in perspective with ruthenium catalysts?555 CHF/g456Grubbs III(G-III)
6. 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, 2039-2041.For G-II : Scholl, M.; Trnka, T.M.; Morgan, J.P.; Grubbs, R.H., Tetrahedron Lett. 1999, 40, 2247-2250.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, 4038-4040.For Piers: Romero, P. E.; Piers, W. E.; McDonald, R. Angew. Chem. Int. Ed. 2004, 43, 6161-6165.For Stewart-Grubbs: Stewart, I. C.; Douglas, C. J.; Grubbs, R. H. Org. Lett. 2008, 10, 441-444.G-IG-IIG-IIIHG-IHG-II167 CHF/g3505612 CHF/g343582 CHF/g3279392 CHF/g1392555 CHF/g456Price on Sigma-AldrichNumber of ref on SciFindernitro-Grela2924 CHF/g1603500 CHF/g315Piers II(P-II)605 CHF/g24Stewart-Grubbs690 CHF/g96GrelaP-IIS-GSchrock