108 / 2023-10-05 18:08:49

Ni-catalyzed asymmetric synthesis of P-chiral phosphines

P-stereogenic; asymmetric catalysis; regioselectivity; enantioconvergence

Phosphorus in Synthetic Chemistry > 3) Syntheses of Chiral organophosphorus compounds

Chiral phosphorus compounds have found important applications in asymmetric catalysis, medicinal chemistry, agromedical chemistry, and other fields. However, the synthesis of these compounds poses significant challenges. This abstract introduces our initial progress in the asymmetric synthesis of chiral phosphine compounds.^1-5 A series of transformations of SPO have achieved by P-C bond formations. Through in-situ reduction, the asymmetric transformations of air-sensitive and toxic secondary phosphines were also realized. During the investigation, a rare phenomenon of direct enantioconvergence has been discovered in the synthesis of allenylphoshines. Under the catalysis of Ni(II), a pair of enantiomers of racemic propargylic esters underwent different reaction pathways to obtain the same product without racemization or symmetrization of the racemic esters. In addition, based on the previous mechanistic studies of hydrophosphorylation reaction, we achieved the hydrosulfenation reaction of sulfenic acid (prepared in situ) and alkynes, obtaining medicinal relevant alkenyl sulfoxides with a broad scope.⁶