Deciphering the origin of enantioselectivity on the cis-cyclopropanation of styrene with enantiopure dichloro,di-gold(I)-SEGPHOS carbenoids generated from propargylic esters.

08:00 EDT 16th May 2019 | BioPortfolio

Summary of "Deciphering the origin of enantioselectivity on the cis-cyclopropanation of styrene with enantiopure dichloro,di-gold(I)-SEGPHOS carbenoids generated from propargylic esters."

The stereoselective synthesis of cis-disubstituted cyclopropanes by the Au(I)/PPh3-catalyzed cycloaddition of propargylic esters and styrene has been studied using density functional theory calculations. The computed mechanistic scheme involves the rate-limiting 1,2-rearrangement of the propargylic ester with the π-coordinated gold complex, followed by the (2+1)-cheletropic reaction of styrene with the alkenyl-Au(I) carbene intermediate to afford the cis-disubstituted cyclopropane derivative in a high cis/trans diastereomeric ratio. With (R)-di-chloro,di-gold-SEGPHOS complex as catalyst, computations are consistent with a rate-determining (2+1)-cheletropic reaction, in which facial discrimination is proposed to result from a combination of subtle steric and electronic effects in the SiRe facial approach transition structure, which favor the formation of the cis-cyclopropane diastereomer of 1R,2S absolute configuration, as experimentally observed.


Journal Details

This article was published in the following journal.

Name: The Journal of organic chemistry
ISSN: 1520-6904


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