The Baeyer -Villiger (BV) oxidation1 is highly valuable for the synthesis of esters or lactones. Especially, the asymmetric BV oxidation of racemic or prochiral cyclic ketones provides a simple and attractive route for the synthesis of optically active lactones. we have successfully developed highly enantioselective BV oxidations of both prochiral and racemic cyclic ketones using chiral N, N' -dioxide-ScIII complex2 catalysts in a common solvent (ethyl acetate). The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active e- and ?-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile, the kinetic resolution of racemic 2-arylcyclohexanones was also realized via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones, whose formation is counter to the migratory aptitude, were obtained preferentially. Both the lactones (up to 98% ee value) and the unreacted ketones (up to 99% ee value) were obtained with excellent enantioselectivities.3 References (1) Baeyer, A.; Villiger, V. Ber. Dtsch. Chem. Ges. 1899 , 32, 3625.(2) Liu, X. H.; Lin, L. L.; Feng, X. M. Acc. Chem. Res. 2011 , 44, 574.(3) Zhou, L.; Liu, X. H.; Ji, J.; Zhang, Y. H.; Hu, X. L.; lin, L. L.; Feng, X. M. J. Am. Chem. Soc. 2012 , 134, 17023.

Enantioselective Baeyer-Villiger oxidation: Desymmetrization of prochiral cyclic ketones and kinetic resolution of racemic 2-arylcyclohexanones

246th National Meeting (2013)

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