80. Glueck, D. S. Catalytic Asymmetric Synthesis of
P-Stereogenic
Phosphines:
Beyond
Precious
Metals. Synlett2021, 32,
875-884.
Abstract
Metal-catalyzed
asymmetric synthesis of P-stereogenic phosphines is a
potentially useful approach to a class of chiral ligands with
valuable applications in asymmetric catalysis. We introduced
this idea with chiral platinum and palladium catalysts,
exploiting rapid pyramidal inversion in diastereomeric
metal–phosphido complexes (ML*(PRR′)) to control phosphorus
stereochemistry. This Account summarizes our attempts to develop
related synthetic methods using earth-abundant metals,
especially copper, in which weaker metal–ligand bonds and faster
substitution processes were expected to result in more active
catalysts. Indeed, precious metals were not required. Without
any transition metals at all, we exploited related
P-epimerization processes to prepare enantiomerically pure
phosphiranes and secondary phosphine oxides (SPOs) from
commercially available chiral epoxides.
