Copper-Mediated Formation of Aryl, Heteroaryl, Vinyl and Alkynyl Difluoromethylphosphonates: A General Approach to Fluorinated Phosphate Mimics
Maria V. Ivanova
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Alexandre Bayle
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Tatiana Besset
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Search for more papers by this authorCorresponding Author
Dr. Thomas Poisson
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)Search for more papers by this authorProf. Dr. Xavier Pannecoucke
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Search for more papers by this authorMaria V. Ivanova
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Alexandre Bayle
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
These authors contributed equally to this work.
Search for more papers by this authorDr. Tatiana Besset
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Search for more papers by this authorCorresponding Author
Dr. Thomas Poisson
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)Search for more papers by this authorProf. Dr. Xavier Pannecoucke
Normandie Univ., COBRA, UMR 6014 et FR 3038, Univ. Rouen, INSA Rouen, CNRS, 1 rue Tesnière, 76821 Mont Saint-Aignan Cedex (France)
Search for more papers by this authorGraphical Abstract
A general approach to aryl, heteroaryl, vinyl, and alkynyl difluoromethylphosphonates was developed providing access to a broad range of products including biologically relevant molecules in good to excellent yields. Mechanistic studies suggest the involvement of a copper(III) species as key intermediate.
Abstract
A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2PO(OEt)2, iodonium salts and a copper salt provided a straightforward manifold to reach these highly relevant products. The reaction proved to be highly functional group tolerant and proceeded under mild conditions, giving the corresponding products in good to excellent yields. This method represents the first general synthetic route to this important class of fluorinated scaffolds, which are well-recognized as in vivo stable phosphate surrogates.
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