Evolution of a 'privileged' P-alkene ligand: added planar chirality beats BINOL axial chirality in catalytic asymmetric C-C bond formation

Alkene planar chirality is introduced in the 'privileged' P-alkene phosphoramidite ligand 1. The resulting diastereomeric ligands (pR,R)-5 and (pS,R)-5 form optically pure complexes of Rh(i) and Pd(ii), which catalyze conjugate additions of boron C-nucleophiles to enones and allylic alkylations, respectively. In the Rh-catalyzed reaction, the planar chirality of the alkene exerts absolute enantiocontrol over the potent BINOL auxiliary. Planar chirality is introduced in a 'privileged' P-alkene phosphoramidite ligand and shown to overwhelm the chirality of the BINOL auxiliary.

Automated summary

Alkene planar chirality is introduced in the 'privileged' P-alkene phosphoramidite ligand, resulting in optically pure complexes of Rh(i) and Pd(ii). These complexes catalyze conjugate additions of boron C-nucleophiles to enones and allylic alkylations, respectively. The planar chirality of the alkene exhibits absolute enantiocontrol over the BINOL auxiliary in the Rh-catalyzed reaction.