Synthesis 2017; 49(15): 3444-3452
DOI: 10.1055/s-0036-1588499
short review
© Georg Thieme Verlag Stuttgart · New York

Metal-Free Generation of Phosphorus-Centered Radicals for the Synthesis of Phosphorus-Based Heterocycles: A Personal Account

Valentin Quint
a  Normandie Université, Laboratoire de Chimie Moléculaire et Thio-organique, CNRS-UMR 6507, ENSICAEN, Université de Caen Normandie, 6 Boulevard du Maréchal Juin, 14000 Caen, France   Email: [email protected]
,
Ludovik Noël-Duchesneau
a  Normandie Université, Laboratoire de Chimie Moléculaire et Thio-organique, CNRS-UMR 6507, ENSICAEN, Université de Caen Normandie, 6 Boulevard du Maréchal Juin, 14000 Caen, France   Email: [email protected]
,
Elodie Lagadic
a  Normandie Université, Laboratoire de Chimie Moléculaire et Thio-organique, CNRS-UMR 6507, ENSICAEN, Université de Caen Normandie, 6 Boulevard du Maréchal Juin, 14000 Caen, France   Email: [email protected]
,
Fabrice Morlet-Savary
b  Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15 rue Jean Starcky, 68057 Mulhouse Cedex, France
,
Jacques Lalevée
b  Institut de Science des Matériaux de Mulhouse IS2M, UMR CNRS 7361, UHA, 15 rue Jean Starcky, 68057 Mulhouse Cedex, France
,
Annie- Claude Gaumont
a  Normandie Université, Laboratoire de Chimie Moléculaire et Thio-organique, CNRS-UMR 6507, ENSICAEN, Université de Caen Normandie, 6 Boulevard du Maréchal Juin, 14000 Caen, France   Email: [email protected]
,
Sami Lakhdar*
a  Normandie Université, Laboratoire de Chimie Moléculaire et Thio-organique, CNRS-UMR 6507, ENSICAEN, Université de Caen Normandie, 6 Boulevard du Maréchal Juin, 14000 Caen, France   Email: [email protected]
› Author Affiliations
The authors thank the CNRS, Normandie Université and Labex Synorg (ANR-11-LABX-0029) for financial support. V.Q. is grateful to the ‘Ministère de l’Enseignement supérieur et de la Recherche’ for a fellowship.
Further Information

Publication History

Received: 29 May 2017

Accepted after revision: 26 June 2017

Publication Date:
13 July 2017 (online)


Dedicated to Prof. Herbert Mayr on the occasion of his 70th birthday

Abstract

This short review describes our recent efforts to generate phosphorus-based radicals under metal-free conditions and their use as key intermediates for the synthesis of phosphorus-based heterocycles. In this regard, the synthesis of benzo[b]phosphole oxides and 6-phosphorylated phenanthridines will be reported. While the synthesis of the former lies in the use of photoredox catalysis, the latter have been obtained through the use of an electron donor–acceptor complex from the combination of diphenyliodonium ion with triethylamine. Mechanistic aspects of both reaction types are discussed based on detailed mechanistic studies including electron paramagnetic resonance, UV–vis spectroscopic, NMR and steady-state photolysis experiments.

1 Introduction

2 Photoredox Catalysis for the Generation of Phosphinoyl Radicals

3 Generation of Phosphinoyl Radicals through the Formation of EDA Complexes

4 Conclusions

 
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