Author, as appears in the article.: Herle, Bart; Holstein, Philipp M.; Echavarren, Antonio M.;
Department: Química Analítica i Química Orgànica
URV's Author/s: ECHAVARREN PABLOS, ANTONIO
Keywords: Vinylcyclopropanes Retro-buchner reaction Gold catalysis Cyclopropanation Cycloheptatrienes retro-buchner reaction gold catalysis cyclopropanation cycloheptatrienes
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.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Engenharias ii Ciências agrárias i Chemistry, physical Chemistry (miscellaneous) Chemistry (all) Catalysis Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: antoniomaria.echavarren@urv.cat
Author identifier: 0000-0002-6418-7930
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acscatal.7b00737
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Acs Catalysis. 7 (5): 3668-3675
APA: Herle, Bart; Holstein, Philipp M.; Echavarren, Antonio M.; (2017). Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions. Acs Catalysis, 7(5), 3668-3675. DOI: 10.1021/acscatal.7b00737
Article's DOI: 10.1021/acscatal.7b00737
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
Publication Type: Journal Publications
Repositori URV