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
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/acscatal.7b00737
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
First page: 3668
Publication Type: Article Artículo Article
Repositori URV