Preparation and Regioselective SN2‘ Reaction of Novel gem-Difluorinated Vinyloxiranes with RLi
- 24 September 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 69 (22), 7616-7627
- https://doi.org/10.1021/jo049025x
Abstract
A series of hitherto unknown 3,4-epoxy-1,1-difluorobutenes were prepared from the readily accessible α,β-epoxy ketones and these compounds were found to undergo regioselective SN2‘ reactions with hard RLi nucleophiles occurring at the highly positively charged terminal fluorine-possessing sp2 carbon atom in quite sharp contrast to the cases of the corresponding nonfluorinated vinyloxiranes which only attained a low level of regioselectivity. Addition of HMPA substantially improved the products' olefinic stereoselectivity. Theoretical calculations were used to qualitatively explore the nature of selectivity in these reactions.Keywords
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