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Stereospecific Ring Contraction of Bromocycloheptenes through Dyotropic Rearrangements via Nonclassical Carbocation-Anion Pairs.
- Author(s): Goh, Shermin S
- Champagne, Pier Alexandre
- Guduguntla, Sureshbabu
- Kikuchi, Takashi
- Fujita, Makoto
- Houk, KN
- Feringa, Ben L
- et al.
Published Web Location
https://doi.org/10.1021/jacs.8b00821Abstract
Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.
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