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Origin of Stereoselectivity in a Chiral N-Heterocyclic Carbene-Catalyzed Desymmetrization of Substituted Cyclohexyl 1,3-Diketones
DSpace at IIT Bombay
View Archive Info| Field | Value | |
| Title |
Origin of Stereoselectivity in a Chiral N-Heterocyclic Carbene-Catalyzed Desymmetrization of Substituted Cyclohexyl 1,3-Diketones
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| Creator |
REDDI, Y
SUNOJ, RB |
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| Subject |
MECHANISM
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| Description |
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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| Publisher |
AMER CHEMICAL SOC
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| Date |
2014-10-15T11:47:29Z
2014-10-15T11:47:29Z 2012 |
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| Type |
Article
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| Identifier |
ORGANIC LETTERS, 14(11)2810-2813
http://dx.doi.org/10.1021/ol301036u http://dspace.library.iitb.ac.in/jspui/handle/100/14825 |
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| Language |
en
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