Kharasch–Sosnovsky reaction

The Kharasch–Sosnovsky reaction is a method that involves using a copper or cobalt salt as a catalyst to oxidize olefins at the allylic position, subsequently condensing a peroxy ester (e.g. tert-Butyl peroxybenzoate) or a peroxide resulting in the formation of allylic benzoates or alcohols via radical oxidation.[1] This method is noteworthy for being the first allylic functionalization to utilize first-row transition metals and has found numerous applications in chemical and total synthesis.[2] Chiral ligands can be used to render the reaction asymmetric, constructing chiral C–O bonds via C–H bond activation.[3] This is notable as asymmetric addition to allylic groups tends to be difficult due to the transition state being highly symmetric. The reaction is named after Morris S. Kharasch and George Sosnovsky who first reported it in 1958.[4] This method is noteworthy for being the first allylic functionalization to utilize first-row transition metals and has found numerous applications in chemical and total synthesis.[2]

  1. ^ (a) Kharasch, M. S., & Sosnovsky, G. (1958). The Reactions of t-Butyl Perbenzoate and Olefins−a Stereospecific Reaction. Journal of the American Chemical Society, 80, 756−756. doi:10.1021/ja01536a062
    (b) Kharasch, M. S., Sosnovsky, G., & Yang, N. C. (1959). Reactions of t-Butyl Peresters: The Reaction of Peresters with Olefins. Journal of the American Chemical Society, 81, 5819−5824. doi:10.1021/ja01530a067
    (c) Beckwith, A. L. J., & Zavitsas, A. A. (1986). Allylic Oxidations by Peroxy Esters Catalyzed by Copper Salts. The Potential for Stereoselective Syntheses. Journal of the American Chemical Society, 108, 8230−8234. doi:10.1021/ja00286a020
  2. ^ a b Zweig, J. E., Kim, D. E., & Newhouse, T. R. (2017). Methods Utilizing First-Row Transition Metals in Natural Product Total Synthesis. Chemical Reviews, 117, 11680−11752. doi:10.1021/acs.chemrev.6b00833
  3. ^ k. Mikami and M. Lautens (2007). New Frontiers in Asymmetric Catalysis. Wiley. p. 142. ISBN 9780470097991.
  4. ^ Kharasch, M. S.; Sosnovsky, George (February 1958). "THE REACTIONS OF t-BUTYL PERBENZOATE AND OLEFINS—A STEREOSPECIFIC REACTION". Journal of the American Chemical Society. 80 (3): 756. Bibcode:1958JAChS..80..756K. doi:10.1021/ja01536a062.
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