%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