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Stereoselective Gold(I)‐Catalyzed Vinylcyclopropanation via Generation of a Sulfur‐Substituted Vinyl Carbene Equivalent
Author(s) -
Yuan Tengrui,
Ryckaert Bram,
Van Hecke Kristof,
Hullaert Jan,
Winne Johan M.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202012664
Subject(s) - carbene , cyclopropanation , cyclopropane , chemistry , cyclopentene , stereoselectivity , propargyl , thio , sulfonium , catalysis , organic chemistry , medicinal chemistry , combinatorial chemistry , ring (chemistry) , salt (chemistry)
A stereoselective gold(I)‐catalyzed vinylcyclopropanation of alkenes has been developed. A gold‐coordinated cationic vinyl carbene species, readily generated via a rearrangement of the ethylenedithioacetal of propargyl aldehyde, reacts with a wide range of alkenes to afford thio‐substituted vinylcyclopropanes. The gold‐catalyzed vinyl cyclopropanation proceeds under mild conditions at room temperature and is generally selective for the formation of cis ‐substituted cyclopropanes. The reaction allows the formal introduction of a “naked” vinyl carbene, by subsequent chemoselective hydrodesulfurisation of the ethylenedithio‐bridge. The synthetic utility of the new method is demonstrated by a short, racemic formal synthesis of the alkaloid cephalotaxin, hinging on a key vinyl cyclopropane‐cyclopentene rearrangement.