Cargando…

Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles

A chromium-catalyzed, visible light-activated net [4 + 2] cycloaddition between dienes and electron-deficient alkenes is described. Gathered evidence, via control experiments, isolated intermediates, and measured redox potentials, points to several converging reaction pathways that afford the cycloh...

Descripción completa

Detalles Bibliográficos
Autores principales: Stevenson, Susan M., Higgins, Robert F., Shores, Matthew P., Ferreira, Eric M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5297334/
https://www.ncbi.nlm.nih.gov/pubmed/28451213
http://dx.doi.org/10.1039/c6sc03303b
_version_ 1782505720584863744
author Stevenson, Susan M.
Higgins, Robert F.
Shores, Matthew P.
Ferreira, Eric M.
author_facet Stevenson, Susan M.
Higgins, Robert F.
Shores, Matthew P.
Ferreira, Eric M.
author_sort Stevenson, Susan M.
collection PubMed
description A chromium-catalyzed, visible light-activated net [4 + 2] cycloaddition between dienes and electron-deficient alkenes is described. Gathered evidence, via control experiments, isolated intermediates, and measured redox potentials, points to several converging reaction pathways that afford the cyclohexene adducts, including a photochemical [2 + 2] cycloaddition/vinylcyclobutane rearrangement cascade and a substrate excitation/oxidation sequence to a radical cation intermediate. Notably, the accompanying mechanistic stipulations result in a process that yields regioisomeric compounds from those generated by traditional Diels–Alder cycloadditions.
format Online
Article
Text
id pubmed-5297334
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher Royal Society of Chemistry
record_format MEDLINE/PubMed
spelling pubmed-52973342017-04-27 Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles Stevenson, Susan M. Higgins, Robert F. Shores, Matthew P. Ferreira, Eric M. Chem Sci Chemistry A chromium-catalyzed, visible light-activated net [4 + 2] cycloaddition between dienes and electron-deficient alkenes is described. Gathered evidence, via control experiments, isolated intermediates, and measured redox potentials, points to several converging reaction pathways that afford the cyclohexene adducts, including a photochemical [2 + 2] cycloaddition/vinylcyclobutane rearrangement cascade and a substrate excitation/oxidation sequence to a radical cation intermediate. Notably, the accompanying mechanistic stipulations result in a process that yields regioisomeric compounds from those generated by traditional Diels–Alder cycloadditions. Royal Society of Chemistry 2017-01-01 2016-09-12 /pmc/articles/PMC5297334/ /pubmed/28451213 http://dx.doi.org/10.1039/c6sc03303b Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License (http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
Stevenson, Susan M.
Higgins, Robert F.
Shores, Matthew P.
Ferreira, Eric M.
Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title_full Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title_fullStr Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title_full_unstemmed Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title_short Chromium photocatalysis: accessing structural complements to Diels–Alder adducts with electron-deficient dienophiles
title_sort chromium photocatalysis: accessing structural complements to diels–alder adducts with electron-deficient dienophiles
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5297334/
https://www.ncbi.nlm.nih.gov/pubmed/28451213
http://dx.doi.org/10.1039/c6sc03303b
work_keys_str_mv AT stevensonsusanm chromiumphotocatalysisaccessingstructuralcomplementstodielsalderadductswithelectrondeficientdienophiles
AT higginsrobertf chromiumphotocatalysisaccessingstructuralcomplementstodielsalderadductswithelectrondeficientdienophiles
AT shoresmatthewp chromiumphotocatalysisaccessingstructuralcomplementstodielsalderadductswithelectrondeficientdienophiles
AT ferreiraericm chromiumphotocatalysisaccessingstructuralcomplementstodielsalderadductswithelectrondeficientdienophiles