Copper‐Mediated Formation of Aryl, Heteroaryl, Vinyl and Alkynyl Difluoromethylphosphonates: A General Approach to Fluorinated Phosphate Mimics. Issue 45 (11th September 2015)

• Record Type: Journal Article
• Authors: Ivanova, Maria V.; Bayle, Alexandre; Besset, Tatiana; Poisson, Thomas; Pannecoucke, Xavier
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 45(2015)
• Page Start: 13406
• Page End: 13410
• Publication Date: 2015-09-11
• Subjects: copper -- fluorine -- iodonium salts -- phosphate mimic -- synthetic method; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201507130
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A general and efficient access to aryl, heteroaryl, vinyl and alkynyl difluoromethylphosphonates is described. The developed methodology using TMSCF2 PO(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. 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.