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Metal-Free Deoxygenation of Amine N-Oxides: Synthetic and Mechanistic Studies |
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| Authors: | Dr William Lecroq Jules Schleinitz Mallaury Billoue Anna Perfetto Prof Dr Annie-Claude Gaumont Prof Jacques Lalevée Dr Ilaria Ciofini Dr Laurence Grimaud Dr Sami Lakhdar |
| Institution: | 1. Normandie Univ., LCMT, ENSICAEN, UNICAEN, CNRS, 6, Boulevard Maréchal Juin, Caen, 14000 France
These authors contributed equally to this work;2. Laboratoire des biomolécules, LBM, Département de chimie, École normale supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France These authors contributed equally to this work;3. Normandie Univ., LCMT, ENSICAEN, UNICAEN, CNRS, 6, Boulevard Maréchal Juin, Caen, 14000 France;4. Institute of Chemistry for Life and Health Sciences (i-CLeHS) Chimie ParisTech, PSL University, CNRS, 11 rue P. et M. Curie, 75005 Paris, France;5. Université de Haute-Alsace, CNRS, IS2M UMR 7361, 68100 Mulhouse, France;6. Laboratoire des biomolécules, LBM, Département de chimie, École normale supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France;7. Université Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069), 118 Route de Narbonne, 31062 Toulouse Cedex 09, France |
| Abstract: | We report herein an unprecedented combination of light and P(III)/P(V) redox cycling for the efficient deoxygenation of aromatic amine N-oxides. Moreover, we discovered that a large variety of aliphatic amine N-oxides can easily be deoxygenated by using only phenylsilane. These practically simple approaches proceed well under metal-free conditions, tolerate many functionalities and are highly chemoselective. Combined experimental and computational studies enabled a deep understanding of factors controlling the reactivity of both aromatic and aliphatic amine N-oxides. |
| Keywords: | deoxygenation mechanisms photochemistry organocatalysis selectivity |