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

Reddi, Yernaidu ; Sunoj, Raghavan B. (2012) Origin of stereoselectivity in a chiral N-heterocyclic carbene-catalyzed desymmetrization of substituted cyclohexyl 1,3-diketones Organic Letters, 14 (11). pp. 2810-2813. ISSN 1523-7060

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ol301036u

Related URL: http://dx.doi.org/10.1021/ol301036u

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.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:109768
Deposited On:02 Aug 2017 11:51
Last Modified:02 Aug 2017 11:51

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