%0 Generic
%A Herlé, Bart
%A Holstein, Philipp M.
%A Echavarren, Antonio M.
%D 2017
%T Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
%U https://acs.figshare.com/articles/dataset/Stereoselective_i_cis_i_-Vinylcyclopropanation_via_a_Gold_I_-Catalyzed_Retro-Buchner_Reaction_under_Mild_Conditions/4904033
%R 10.1021/acscatal.7b00737.s002
%2 https://acs.figshare.com/ndownloader/files/8245412
%K retro-Buchner reaction
%K stereochemical model
%K Mild Conditions
%K substrates proceeds
%K gold-catalyzed isomerization
%K alkene
%K DFT calculations
%K 7-
%K cis selectivity
%K cycloheptatriene derivatives
%K Stereoselective cis
%K Allylic gold carbenes
%K form vinylcyclopropanes
%X 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.
%I ACS Publications