Author, as appears in the article.: Echavarren, A.M.; Herlé, B.; Holstein, P.M.

Department: Química Analítica i Química Orgànica

URV's Author/s: ECHAVARREN PABLOS, ANTONIO MARIA; Herlé, B.; Holstein, P.M.

Keywords: cycloheptatrienes cyclopropanation Gold catalysis

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 Química Chemistry

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 2155-5435

Author identifier: 0000-0001-6808-3007; ;

Record's date: 2017-10-19

Last page: 3675

Journal volume: 7

Papper version: info:eu-repo/semantics/publishedVersion

Link to the original source: http://pubs.acs.org/doi/abs/10.1021/acscatal.7b00737

Funding program: euratom; European Research Council; ERC; 321066 european; MINECO/FEDER, UE; CTQ2016-75960-P MINECO-Severo Ochoa Excellence Acreditation 2014-2018; SEV; SEV-2013-0319 altres; Grups consolidats Generalitat de Catalunya; SGR; 2014 SGR 818

Article's DOI: 10.1021/acscatal.7b00737

Entity: Universitat Rovira i Virgili

Journal publication year: 2017

First page: 3668

Publication Type: Article Artículo Article