Stereospecific construction of chiral tertiary and quaternary carbon by nucleophilic cyclopropanation with bis(iodozincio)methane

Chemistry, an Asian Journal
Kenichi Nomura, Seijiro Matsubara

Abstract

The reaction of a ketone having a leaving group at the alpha-position, such as alpha,beta-epoxy ketone or alpha-sulfonyloxy ketone, with bis(iodozincio)methane affords a zinc alkoxide of cyclopropanol. The reaction proceeds by nucleophilic addition of the dizinc to the carbonyl group and a sequential intramolecular nucleophilic substitution of the introduced iodozinciomethyl group to the adjacent electrophilic carbon that has a leaving group. When an optically active alpha,beta-epoxy ketone or alpha-sulfonyloxy ketone is treated with the dizinc, a zinc alkoxide of cyclopropanol having a chiral tertiary or quaternary carbon in the cyclopropane ring is obtained, and the obtained zinc alkoxide of cyclopropanol acts as a chiral homoenolate. When it is treated with an electrophile in the presence of copper cyanide, it gives an optically active alpha-tertiary or -quaternary ketone that retains high optical purity.

References

Oct 31, 2002·Angewandte Chemie·Jens Christoffers, Alexander Mann
Apr 29, 2006·Angewandte Chemie·Darunee Soorukram, Paul Knochel

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Citations

Jan 23, 2016·Journal of the American Chemical Society·Olaf CussóMiquel Costas
Aug 22, 2012·Angewandte Chemie·Pragna Pratic DasJin Kun Cha
Nov 11, 2014·Organic & Biomolecular Chemistry·Ryosuke HaraguchiSeijiro Matsubara
Apr 26, 2018·Chemistry : a European Journal·Ilan MarekMarwan Simaan
Mar 17, 2021·Journal of the American Chemical Society·Yoshiya Sekiguchi, Naohiko Yoshikai
Apr 6, 2011·Organic Letters·Kevin ChengPatrick J Walsh
Aug 16, 2017·Journal of the American Chemical Society·L Reginald MillsSophie A L Rousseaux
Mar 27, 2013·Organic Letters·Bibhuti Bhusan ParidaJin Kun Cha
Oct 22, 2020·Chemical Reviews·Tyler R McDonaldSophie A L Rousseaux

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