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Published September 17, 2003 | Supplemental Material
Journal Article Open

A General Model for Selectivity in Olefin Cross Metathesis


In recent years, olefin cross metathesis (CM) has emerged as a powerful and convenient synthetic technique in organic chemistry; however, as a general synthetic method, CM has been limited by the lack of predictability in product selectivity and stereoselectivity. Investigations into olefin cross metathesis with several classes of olefins, including substituted and functionalized styrenes, secondary allylic alcohols, tertiary allylic alcohols, and olefins with α-quaternary centers, have led to a general model useful for the prediction of product selectivity and stereoselectivity in cross metathesis. As a general ranking of olefin reactivity in CM, olefins can be categorized by their relative abilities to undergo homodimerization via cross metathesis and the susceptibility of their homodimers toward secondary metathesis reactions. When an olefin of high reactivity is reacted with an olefin of lower reactivity (sterically bulky, electron-deficient, etc.), selective cross metathesis can be achieved using feedstock stoichiometries as low as 1:1. By employing a metathesis catalyst with the appropriate activity, selective cross metathesis reactions can be achieved with a wide variety of electron-rich, electron-deficient, and sterically bulky olefins. Application of this model has allowed for the prediction and development of selective cross metathesis reactions, culminating in unprecedented three-component intermolecular cross metathesis reactions.

Additional Information

© 2003 American Chemical Society. Received December 31, 2002. Publication Date (Web): August 20, 2003. The authors would like to thank Prof. Helen E. Blackwell, Dr. John P. Morgan, Dr. Steven D. Goldberg, Dr. Brian T. Connell, Prof. F. Dean Toste, and Prof. Justin P. Gallivan for helpful discussions and encouragement. The authors gratefully acknowledge the generous funding provided by the National Institutes of Health.

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