A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine

We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole...

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Detalles Bibliográficos
Autores principales: Li, Guo-Xing, Morales-Rivera, Cristian A., Gao, Fang, Wang, Yaxin, He, Gang, Liu, Peng, Chen, Gong
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5635418/
https://www.ncbi.nlm.nih.gov/pubmed/29081950
http://dx.doi.org/10.1039/c7sc02773g
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author Li, Guo-Xing
Morales-Rivera, Cristian A.
Gao, Fang
Wang, Yaxin
He, Gang
Liu, Peng
Chen, Gong
author_facet Li, Guo-Xing
Morales-Rivera, Cristian A.
Gao, Fang
Wang, Yaxin
He, Gang
Liu, Peng
Chen, Gong
author_sort Li, Guo-Xing
collection PubMed
description We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C–H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl–OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H(2)O or CH(3)CN cosolvent is presented.
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spelling pubmed-56354182017-10-27 A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine Li, Guo-Xing Morales-Rivera, Cristian A. Gao, Fang Wang, Yaxin He, Gang Liu, Peng Chen, Gong Chem Sci Chemistry We report a unified photoredox-catalysis strategy for both hydroxylation and amidation of tertiary and benzylic C–H bonds. Use of hydroxyl perfluorobenziodoxole (PFBl–OH) oxidant is critical for efficient tertiary C–H functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Benzylic methylene C–H bonds can be hydroxylated or amidated using unmodified hydroxyl benziodoxole oxidant Bl–OH under similar conditions. An ionic mechanism involving nucleophilic trapping of a carbocation intermediate by H(2)O or CH(3)CN cosolvent is presented. Royal Society of Chemistry 2017-10-01 2017-09-04 /pmc/articles/PMC5635418/ /pubmed/29081950 http://dx.doi.org/10.1039/c7sc02773g Text en This journal is © The Royal Society of Chemistry 2017 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
Li, Guo-Xing
Morales-Rivera, Cristian A.
Gao, Fang
Wang, Yaxin
He, Gang
Liu, Peng
Chen, Gong
A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title_full A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title_fullStr A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title_full_unstemmed A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title_short A unified photoredox-catalysis strategy for C(sp(3))–H hydroxylation and amidation using hypervalent iodine
title_sort unified photoredox-catalysis strategy for c(sp(3))–h hydroxylation and amidation using hypervalent iodine
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5635418/
https://www.ncbi.nlm.nih.gov/pubmed/29081950
http://dx.doi.org/10.1039/c7sc02773g
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