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Olefin Cross Metathesis Christopher Kendall March 20, 2006 The metathesis review: Handbook of Metathesis Grubbs, R. H., ed.; Wiley-VCH: Weinheim, 2003 Metathesis in total synthesis: Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem. Int. Ed. 2005, 44, 4490
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The nobel prize in chemistry, 2005 “Considering the short time during which Grubbs’ and Schrock’s catalysts have been available, the breadth of applications, is truly remarkable.” Prof. Per Ahlberg Nobel Committee for Chemistry "for the development of the metathesis method in organic synthesis" Yves ChauvinRobert H. GrubbsRichard R. Schrock
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Commercial Metathesis
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Articles cited on Web of Science, topic = “cross metathesis” Olefin Cross Metathesis (CM) review in Handbook of Metathesis by Chatterjee, A. K. (chapter 2.8, Vol. 2 pp. 246-295) review covering 1998-2002: Connon, S. J.; Blechert, S. Angew. Chem. Int. Ed. 2003, 42, 1900 Cross-metathesis methodologies have recently been shown to be highly effective in the synthesis of insect pheromones, polymer additives, and fine chemicals, i.e., valuable synthetic intermediates such as novel , -unsaturated carbonyl systems. Pederson, R. L. in Handbook of Metathesis Vol. 2 p 491
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The mechanism
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The Catalysts
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The key reference Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360 Type I terminal olefins 1° allylic alcohols, amines (protected), esters allyl halides, silanes allyl boronate esters, phosphonates, phosphine oxides, sulfides styrenes (no large ortho groups) Type II 2° allylic alcohols, unptrotected 3° allylic alcohols acrylates, acrylamides, acrylic acid, acrolein, vinyl ketones vinyl epoxides perfluorinated alkane olefins styrenes (large ortho substituents) Type III 1,1-disubstituted olefins trisubstituted olefins (non-bulky) 4° allylic carbon 3° allylic alcohol (protected) vinyl phosphonates Type IV vinyl nitro olefins trisubstituted allylic alcohols (protected) For Grubbs II:
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The functionalization of terminal olefins
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cm in natural product synthesis Wang, Y.; Romo, D. Org. Lett. 2002, 4, 3231
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cm in natural product synthesis Bouzbouz, S.; Cossy, J. Org. Lett. 2001, 3, 1451
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cm in natural product synthesis Bouzbouz, S.; Cossy, J. Org. Lett. 2001, 3, 1451
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cm in natural product synthesis Kitamura, T.; Sato, Y.; Mori, M. Tetrahedron 2004, 60, 9649
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cm in natural product synthesis Randl, S.; Blechert, S. J. Org. Chem. 2003, 68, 8879 Ghosh, A. K.; Liu, C. J. Am. Chem. Soc. 2003, 125, 2374
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cm in natural product synthesis Spessard, S. J.; Stoltz, B. M. Org. Lett. 2002, 4, 1943 Cossy, J.; Willis, C.; Bellosta, V.; Bouzbouz, S. J. Org. Chem. 2002, 67, 1982
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cm in natural product synthesis Ferré-Filmon, K.; Delaude, L.; Demonceau, A.; Noels, A. F. Eur. J. Org. Chem. 2005, 3319 Velder, J.; Ritter, S.; Lex, J.; Schmalz, H.-G. Synthesis 2006, 273
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Atom economy of cm vs. altenate reactions
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CM in pharmaceutical synthesis Pederson, R. L.; Fellows, I. M.; Ung, T. A.; Ishihara, H.; Hajela, S. P. Adv. Synth. Catal. 2002, 344, 728
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CM in pharmaceutical synthesis Hsu, M. C.; Junia, A. J.; Haight, A. R.; Zhang, W. J. Org. Chem. 2004, 69, 3907
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cm in natural product synthesis Chlor, R. B.; Nosse, B.; Sörgel, S.; Böhm, C.; Seitz, M.; Reiser, O. Chem. Eur. J. 2003, 9, 260
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Cm in library synthesis Plettenburg, O.; Mui, C.; Bodmer-Narkevitchy, V.; Wong, C.-H. Adv. Synth. Catal. 2002, 344, 622 Centrone, C. A.; Lowary, T. J. Org. Chem. 2002, 67, 8862 Rai, A. N.; Basu, A. J. Org. Chem. 2005, 70, 8228
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Comin, M. J.; Parrish, D. A.; Deschamps, J. R.; Marquez, V. E. Org. Lett. 2006, 8, 705 Galan, M. C.; O’Conner, S. E. Tetrahedron Lett. 2006, 47, 1563 Cm in library synthesis
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cm in natural product synthesis Statsuk, A. V.; Liu, D.; Kozmin, S. A. J. Am. Chem. Soc. 2004, 126, 9546
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cm in natural product synthesis Albert, B. A.; Sivaramakrishnan, A.; Naka, T.; Koide, K. J. Am. Chem. Soc. 2006, 128, 2792
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cm in natural product synthesis Ghosh, A. K.; Gong, G. J. Org. Chem. 2006, 71, 1085
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cm in natural product synthesis Wu, B.; Liu, Q.; Sulikowski, G. A. Angew. Chem. Int. Ed. 2004, 43, 6673
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cm in natural product synthesis Yoshimura, T.; Fakushiji, F.; Kondo, S.; Wu, X.; Shindo, M.; Shishido, K. Org. Lett. 2006, 8, 475 10 steps
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cm in natural product synthesis Crimmins, M. T.; Caussanel, F. J. Am. Chem. Soc. 2006, 128, 3128 8 steps (a) Grubbs II, CH 2 Cl 2, reflux: 68% + 10% Z isomer
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cm in complex molecule synthesis Lera, M.; Hayes, C. J. Org. Lett. 2001, 3, 2765
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cm in complex molecule synthesis Chen, G.; Schmieg, J.; Tsuji, M.; Franck, R. W. Org. Lett. 2004, 6, 4077
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cm in complex molecule synthesis Cho, Y. S.; Wan, Q.; Danishefsky, S. J. Bioorg. Med. Chem. 2005, 13, 5259
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CM in Natural product modification Karama, U.; Höfle, G. Eur. J. Org. Chem. 2003, 1042
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CM in Natural product modification Smith III, A. B.; Rucker, P. V.; Brouard, I.; Freeze, S. B.; Xia, S.; Horwitz, S. B. Org. Lett. 2005, 7, 5199
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CM in Natural product structure determination Tanaka, K.; Nakanishi, K.; Berova, N. J. Am. Chem. Soc. 2003, 125, 10802
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Ene-yne cm review: Diver, S. T.; Giessert, A. J. Synthesis 2003, 466
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Ene-yne cm Royer, F.; Vilain, C.; Elkaïm, L.; Grimaud, L. Org. Lett. 2003, 5, 2007 Ene-yne cm in natural product synthesis Kummer, D. A.; Brenneman, J. B.; Martin, S. F. Org. Lett. 2005, 7, 4621 stepwise: Evans, M. A.; Morken, J. P. Org. Lett. 2005, 7, 3371
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tandem cm reactions
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One-pot cm/intramolecular cycloaddition Hodgson, D. M.; Angrish, D.; Labande, A. H. Chem. Commun. 2006, 627 Tandem ene-yne cm/[4 + 2]cycloaddition Mix, S.; Blechert, S. Org. Lett. 2005, 7, 2015
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Tandem cm in natural product synthesis Quinn, K. J.; Isaacs, A. K.; Arvary, R. A. Org. Lett. 2004, 6, 4143 Michaelis, S.; Blechert, S. Org. Lett. 2005, 7, 5513
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Rom/cm Mihovilovic, M. D.; Grötzl, B.; Kandioller, W.; Snajdrova, R.; Muskotál, A.; Bianchi, D. A.; Stanetty, P. Adv. Synth. Catal. 2006, 348, 463 Weeresakare, G. M.; Liu, Z.; Rainer, J. D. Org. Lett. 2004, 6, 1625
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Rom/cm/rcm Oikawa, M.; Ikoma, M.; Sasaki, M. Tetrahedron Lett. 2005, 46, 5863
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cm in natural product synthesis: ROM/CM/RCM Hart, A. C.; Phillips, A. J. J. Am. Chem. Soc. 2006, 128, 1094
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My favourite example: rom/cm/rcm Takao, K.; Yasui, H.; Yamamoto, S.; Sasaki, D.; Kawasaki, S.; Watanabe, G.; Tadano, K. J. Org. Chem. 2004, 69, 8789
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Alkyne cross metathesis Fürstner, A.; Grela, K.; Mathes, C.; Lehmann, C. W. J. Am. Chem. Soc. 2000, 122, 11799 Fürstner, A.; Mathes, C. Org. Lett. 2002, 3, 221 review: Fürstner, A.; Davies, P. W. Chem. Commun. 2005, 2307
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Alkyne cross metathesis Sashuk, V.; Ignatowska, J.; Grela, K. J. Org. Chem. 2004, 69, 7748
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Asymmetric cm Van Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H. J. Am. Chem. Soc. 2002, 124, 4954 Gillingham, D. G.; Kataoka, O.; Garber, S. B.; Hoveyda, A. H. J. Am. Chem. Soc. 2004, 126, 12288 Schrock, R. R.; Hoveyda, A. H. Angew. Chem. Int. Ed. 2003, 42, 4592 Shawn Collins, Literature Meeting, October 4, 2004 Full Story:
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Cm improvement: catalyst loading Forman, G. S.; Tooze, R. P. J. Organomet. Chem. 2005, 690, 5863 Check Forman 2005 Organomet page ?? Cm improvement: reaction time Bargiggia, F. C.; Merray, W. V. J. Org. Chem. 2005, 70, 9636
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Catalyst delivery vehicle in Cm Hansen, E. C.; Lee, D. Org. Lett. 2004, 6, 2035
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A temporary silicon-tethered rcm Evans, P. A.; Cui, J.; Gharpure, S. J.; Polosukhin, A.; Zhang, H.-R. J. Am. Chem. Soc. 2003, 125, 14702
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summary Cross Metathesis increasingly used as disconnection late in natural product total synthesis Useful tool for library synthesis, especially in biochemical-type applications “Ideal” reaction: a catalytic method for a highly efficient (re: atom economy) C-C bond forming reaction Improvement still possible in catalyst loading, stoichiometry, reaction time/temperature, selectivity, …
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