Origin of stereoselectivity in a chiral N-heterocyclic carbene-catalyzed desymmetrization of substituted cyclohexyl 1,3-diketones

Organic Letters
Yernaidu Reddi, Raghavan B Sunoj

Abstract

The mechanism and stereoselectivity in a chiral N-heterocyclic carbene-catalyzed desymmetrization of a 1,3-diketone is established by using density functional theory computations. The Breslow intermediate formation is identified to involve Hunig's base-assisted proton transfer. The relative energies of stereoselectivity-determining intramolecular aldol cyclization transition states reveal that in the most preferred mode the re-face of enolate adds to the si-face of carbonyl leading to a tricyclic lactone with a configuration (2aS,4aS,8'S) in excellent agreement with previous experimental reports.

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Citations

Jul 31, 2013·Angewandte Chemie·Biplab Maji, Herbert Mayr
Dec 5, 2019·Chemistry : a European Journal·Oldamur Hollóczki
Mar 16, 2021·The Journal of Organic Chemistry·Qi ZhangXinqiang Fang
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Jan 15, 2014·Accounts of Chemical Research·Jessada Mahatthananchai, Jeffrey W Bode
Aug 22, 2017·Journal of the American Chemical Society·Rajat Maji, Steven E Wheeler

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