Cargando…
Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
[Image: see text] 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...
Autores principales: | , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2017
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5424441/ https://www.ncbi.nlm.nih.gov/pubmed/28503355 http://dx.doi.org/10.1021/acscatal.7b00737 |
_version_ | 1783235137930002432 |
---|---|
author | Herlé, Bart Holstein, Philipp M. Echavarren, Antonio M. |
author_facet | Herlé, Bart Holstein, Philipp M. Echavarren, Antonio M. |
author_sort | Herlé, Bart |
collection | PubMed |
description | [Image: see text] 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. |
format | Online Article Text |
id | pubmed-5424441 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-54244412017-05-11 Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions Herlé, Bart Holstein, Philipp M. Echavarren, Antonio M. ACS Catal [Image: see text] 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. American Chemical Society 2017-04-18 2017-05-05 /pmc/articles/PMC5424441/ /pubmed/28503355 http://dx.doi.org/10.1021/acscatal.7b00737 Text en Copyright © 2017 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Herlé, Bart Holstein, Philipp M. Echavarren, Antonio M. Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title | Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title_full | Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title_fullStr | Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title_full_unstemmed | Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title_short | Stereoselective cis-Vinylcyclopropanation
via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions |
title_sort | stereoselective cis-vinylcyclopropanation
via a gold(i)-catalyzed retro-buchner reaction under mild conditions |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5424441/ https://www.ncbi.nlm.nih.gov/pubmed/28503355 http://dx.doi.org/10.1021/acscatal.7b00737 |
work_keys_str_mv | AT herlebart stereoselectivecisvinylcyclopropanationviaagoldicatalyzedretrobuchnerreactionundermildconditions AT holsteinphilippm stereoselectivecisvinylcyclopropanationviaagoldicatalyzedretrobuchnerreactionundermildconditions AT echavarrenantoniom stereoselectivecisvinylcyclopropanationviaagoldicatalyzedretrobuchnerreactionundermildconditions |