A family of gold(I) complexes of composition AuCl(ADAP) (ADAP = alkoxydiaminophosphine) has been prepared through a one-pot simple protocol in which the ADAP ligand is in situ prepared before reaction with the Au(I) source. Structural data demonstrate that these ADAP ligands exert a trans effect superior to those of phosphine or phosphite ligands. Evaluation of the buried volume (%V Bur ) indicates a steric hindrance higher than several NHC-, PR 3 or P(OR 3 ) ligands, in the context of AuCl(L) complexes. These complexes promote the catalytic transfer of a carbene group from ethyl diazoacetate to alkenes and alkanes. In the case of styrene, both the C sp 2-H bonds as well as the C=C bond are functionalized, the relative ratio depending of the catalyst employed, correlating well with the (%V Bur ). Data available allow proposing that these compounds display quite similar electronic properties but differ in steric, a variable that can be readily controlled upon modifying the alkoxy group at the ADAP ligand by simply replacing the starting alcohol employed in their synthesis.

The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)CO 2 Et fragment, which dramatically affects the energy profile of this transformation.

Af amily of phosphine ligands containing af ivemembered ring similar to thep opular N-heterocyclic carbene ligandsa nd an alkoxy third substituent has been developed. Thesea lkoxydiaminophosphinel igands(ADAP) can be generated in one pot and reacted with ac opper(I) source leadingt ot he high yield isolation of complexes[ (ADAP)-CuX] 2 (X = Cl, Br). The dinuclear nature of these compounds has been established by meanso fX-ray studies and DOSY experiments. As creening of the catalytic properties of these complexes toward carbene-transfer reactions from diazocompounds to CÀHb onds (alkane, arene), olefins or NÀH bonds, as wella si nC uAACo rn itrene transfer reactions have shown ap erformance at least similar, if not better,than their (NHC)CuCl analogues,o pening an ew window in copper catalysis with thesereadily tunable ADAP ligands.