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Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes

Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C–H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the prac...

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Autores principales: Zhong, Jian-Ji, To, Wai-Pong, Liu, Yungen, Lu, Wei, Che, Chi-Ming
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6510317/
https://www.ncbi.nlm.nih.gov/pubmed/31160960
http://dx.doi.org/10.1039/c8sc05600e
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author Zhong, Jian-Ji
To, Wai-Pong
Liu, Yungen
Lu, Wei
Che, Chi-Ming
author_facet Zhong, Jian-Ji
To, Wai-Pong
Liu, Yungen
Lu, Wei
Che, Chi-Ming
author_sort Zhong, Jian-Ji
collection PubMed
description Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C–H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the practicability of this approach. Herein we demonstrate that photo-induced oxidative C–H functionalization can be catalysed with high product yields under oxygen-free and acceptorless conditions via inner-sphere atom abstraction by binuclear platinum(ii) diphosphite complexes. Both alcohols (51 examples), particularly the aliphatic ones, and saturated N-heterocycles (24 examples) can be efficiently dehydrogenated under light irradiation at room temperature. Regeneration of the photocatalyst by means of reductive elimination of dihydrogen from the in situ formed platinum(iii)-hydride species represents an alternative paradigm to the current approach in photoredox catalysis.
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spelling pubmed-65103172019-06-03 Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes Zhong, Jian-Ji To, Wai-Pong Liu, Yungen Lu, Wei Che, Chi-Ming Chem Sci Chemistry Although photoredox catalysis employing Ru(ii) and Ir(iii) complexes as photocatalysts has emerged as a versatile tool for oxidative C–H functionalization under mild conditions, the need for additional reagents acting as electron donor/scavenger for completing the catalytic cycle undermines the practicability of this approach. Herein we demonstrate that photo-induced oxidative C–H functionalization can be catalysed with high product yields under oxygen-free and acceptorless conditions via inner-sphere atom abstraction by binuclear platinum(ii) diphosphite complexes. Both alcohols (51 examples), particularly the aliphatic ones, and saturated N-heterocycles (24 examples) can be efficiently dehydrogenated under light irradiation at room temperature. Regeneration of the photocatalyst by means of reductive elimination of dihydrogen from the in situ formed platinum(iii)-hydride species represents an alternative paradigm to the current approach in photoredox catalysis. Royal Society of Chemistry 2019-04-02 /pmc/articles/PMC6510317/ /pubmed/31160960 http://dx.doi.org/10.1039/c8sc05600e Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Zhong, Jian-Ji
To, Wai-Pong
Liu, Yungen
Lu, Wei
Che, Chi-Ming
Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title_full Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title_fullStr Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title_full_unstemmed Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title_short Efficient acceptorless photo-dehydrogenation of alcohols and N-heterocycles with binuclear platinum(ii) diphosphite complexes
title_sort efficient acceptorless photo-dehydrogenation of alcohols and n-heterocycles with binuclear platinum(ii) diphosphite complexes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6510317/
https://www.ncbi.nlm.nih.gov/pubmed/31160960
http://dx.doi.org/10.1039/c8sc05600e
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