Alkoxydiaminophosphine Ligands as Surrogates of NHCs in Copper Catalysis

A family of phosphine ligands containing a five‐membered ring similar to the popular N‐heterocyclic carbene ligands and an alkoxy third substituent has been developed. These alkoxydiaminophosphine ligands (ADAP) can be generated in one pot and reacted with a copper(I) source leading to the high yield isolation of complexes [(ADAP)CuX] 2 (X=Cl, Br). The dinuclear nature of these compounds has been established by means of X‐ray studies and DOSY experiments. A screening of the catalytic properties of these complexes toward carbene‐transfer reactions from diazocompounds to C−H bonds (alkane, arene), olefins or N−H bonds, as well as in CuAAC or nitrene transfer reactions have shown a performance at least similar, if not better, than their (NHC)CuCl analogues, opening a new window in copper catalysis with these readily tunable ADAP ligands.