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Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system

We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpen...

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Autores principales: Huang, Xiaoqiang, Luo, Shipeng, Burghaus, Olaf, Webster, Richard D., Harms, Klaus, Meggers, Eric
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5637358/
https://www.ncbi.nlm.nih.gov/pubmed/29147543
http://dx.doi.org/10.1039/c7sc02621h
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author Huang, Xiaoqiang
Luo, Shipeng
Burghaus, Olaf
Webster, Richard D.
Harms, Klaus
Meggers, Eric
author_facet Huang, Xiaoqiang
Luo, Shipeng
Burghaus, Olaf
Webster, Richard D.
Harms, Klaus
Meggers, Eric
author_sort Huang, Xiaoqiang
collection PubMed
description We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation.
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spelling pubmed-56373582017-11-16 Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system Huang, Xiaoqiang Luo, Shipeng Burghaus, Olaf Webster, Richard D. Harms, Klaus Meggers, Eric Chem Sci Chemistry We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(iii) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation. Royal Society of Chemistry 2017-10-01 2017-09-01 /pmc/articles/PMC5637358/ /pubmed/29147543 http://dx.doi.org/10.1039/c7sc02621h Text en This journal is © The Royal Society of Chemistry 2017 https://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/ (https://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
Huang, Xiaoqiang
Luo, Shipeng
Burghaus, Olaf
Webster, Richard D.
Harms, Klaus
Meggers, Eric
Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title_full Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title_fullStr Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title_full_unstemmed Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title_short Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
title_sort combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5637358/
https://www.ncbi.nlm.nih.gov/pubmed/29147543
http://dx.doi.org/10.1039/c7sc02621h
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