11 research outputs found
Tuning ligand electronics and peripheral substitution on cobalt salen complexes: Structure and polymerisation activity
Solvent-Dependent Dynamic Kinetic Asymmetric Transformation/Kinetic Resolution in Molybdenum-catalyzed Asymmetric Allylic Alkylations
The Mechanistic Basis for Electronic Effects on Enantioselectivity in the (salen)Mn(III)-Catalyzed Epoxidation Reaction
New insights into the mechanism of molybdenum-catalyzed asymmetric alkylation*
Abstract: The major features of the catalytic cycle, including structures of key intermediates, have been determined for the molybdenum-catalyzed asymmetric alkylation. The crystal structure of the π-allyl intermediate exhibits 3-point binding of an anionic ligand. Based on NMR analysis, this species adopts in solution a structure consistent with that observed in the solid state. For the allylic alkylation, the crystal structure predicts the opposite stereochemistry vs. that observed experimentally, which suggests that either the reaction proceeds via a minor isomer (Curtin-Hammett conditions) or with retention of configuration. In addition, CO transfer, promoted by Mo(CO) 6 , has been found to play a key role in catalyst turnover