CONTROL OF ASYMMETRIC INDUCTION IN THE ORGANOMETALLIC SYNTHESIS OF 3-METHYL-(E)-4-HEXEN-2-ONE

Bis(mu-methyl-1,3-dimethyl-eta-3-allylnickel) reacts in the presence of phosphorus(III) ligands (phosphines, phosphites) with CO to give 3-methyl-(E)-4-hexen-2-one. Systematic experiments were performed using chiral ligands containing menthyl or menthoxy groups and different achiral groups on the P atom to determine the influence of ligand structure and concentration on the direction and extent of chiral induction in this ketone synthesis. It could be shown that reversion of enantioselectivity can be obtained not only by the obvious method of reversing the absolute configuration of the ligand ("parity control") but also by modifying the nonchiral substituents of the phosphorus ligand ("complementarity control"). The synthesis, physical, and spectroscopic properties of several new menthyl phosphines and phosphites are reported.