Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions

ACS Catalysis
Bart HerléA M Echavarren

Abstract

A highly stereoselective gold(I)-catalyzed cis-vinylcyclopropanation of alkenes has been developed. Allylic gold carbenes, generated via a retro-Buchner reaction of 7-alkenyl-1,3,5-cycloheptatrienes, react with alkenes to form vinylcyclopropanes. The gold(I)-catalyzed retro-Buchner reaction of these substrates proceeds by simple heating at a temperature much lower than that required for the reaction of 7-aryl-1,3,5-cycloheptatrienes (75 °C vs 120 °C). A newly developed Julia-Kocienski reagent enables the synthesis of the required cycloheptatriene derivatives in one step from readily available aldehydes or ketones. On the basis of mechanistic investigations, a stereochemical model for the cis selectivity was proposed. An unprecedented gold-catalyzed isomerization of cis- to trans-cyclopropanes has also been discovered and studied by DFT calculations.

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Citations

Jun 5, 2018·Angewandte Chemie·Thorsten ScherpfViktoria H Gessner
Dec 19, 2018·Angewandte Chemie·Mauro Mato, Antonio M Echavarren
Jan 25, 2019·Angewandte Chemie·Marc Montesinos-MagranerAbraham Mendoza
Apr 5, 2019·Organic & Biomolecular Chemistry·Mauro MatoAntonio M Echavarren
Apr 20, 2019·Chemistry : a European Journal·Xiang YinAntonio M Echavarren
Oct 2, 2019·Angewandte Chemie·Mohanad A HusseinThanh V Nguyen
Feb 29, 2020·Chemical Science·Ana G Herraiz, Marcos G Suero
Jul 2, 2019·Chemical & Pharmaceutical Bulletin·Shunya MoritaJun-Ichi Matsuo
Jan 21, 2020·Chemical Society Reviews·Dong ZhuShifa Zhu
Nov 7, 2019·Chemical Communications : Chem Comm·Melanie A DrewChristopher J T Hyland
May 7, 2021·Chemical Communications : Chem Comm·Rajdip Chowdhury, Abraham Mendoza
Jul 9, 2021·Journal of the American Chemical Society·Mauro MatoAntonio M Echavarren
Nov 3, 2020·Chemical Reviews·Mauro MatoAntonio M Echavarren
Oct 23, 2018·Journal of the American Chemical Society·Sobi AsakoKazuhiko Takai
Jul 6, 2018·Organic Letters·Mauro MatoAntonio M Echavarren

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