Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer

Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N–H bonds of N-arylamides (bond dissociation free energies ∼ 100 kcal/mol) via concerted proton-coupled electron transfer (PCET) and mediating effi...

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Veröffentlicht in:	Journal of the American Chemical Society 2015-07, Vol.137 (29), p.9226-9229
Hauptverfasser:	Choi, Gilbert J, Knowles, Robert R
Format:	Artikel
Sprache:	eng
Schlagworte:	Alkenes - chemistry Amination Catalysis Electron Transport Iridium - chemistry Phosphates - chemistry Protons Thermodynamics
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container_title	Journal of the American Chemical Society
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creator	Choi, Gilbert J Knowles, Robert R
description	Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N–H bonds of N-arylamides (bond dissociation free energies ∼ 100 kcal/mol) via concerted proton-coupled electron transfer (PCET) and mediating efficient carboamination reactions of the resulting amidyl radicals. This manner of PCET activation, which finds its basis in numerous biological redox processes, enables the formal homolysis of a stronger amide N–H bond in the presence of weaker allylic C–H bonds, a selectivity that is uncommon in conventional molecular H atom acceptors. Moreover, this transformation affords access to a broad range of structurally complex heterocycles from simple amide starting materials. The design, synthetic scope, and mechanistic evaluation of the PCET process are described.
doi_str_mv	10.1021/jacs.5b05377
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This manner of PCET activation, which finds its basis in numerous biological redox processes, enables the formal homolysis of a stronger amide N–H bond in the presence of weaker allylic C–H bonds, a selectivity that is uncommon in conventional molecular H atom acceptors. Moreover, this transformation affords access to a broad range of structurally complex heterocycles from simple amide starting materials. 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subjects	Alkenes - chemistry Amination Catalysis Electron Transport Iridium - chemistry Phosphates - chemistry Protons Thermodynamics
title	Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer
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