Nickel-Catalyzed Asymmetric Hydrogenation of α-Substituted Vinylphosphonates and Diarylvinylphosphine Oxides

Chiral alpha-substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, and ligands. However, their catalytic asymmetric synthesis is still rare. Of the only asymmetric hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth-abundant transition-metal nickel catalyzed asymmetric hydrogenation affording the corresponding chiral ethylphosphine products with up to 99 % yield, 96 % ee (enantiomeric excess) (99 % ee, after recrystallization) and 1000 S/C (substrate/catalyst); this is also the first study on the asymmetric hydrogenation of terminal olefins using a nickel catalyst under a hydrogen atmosphere. The catalytic mechanism was investigated via deuterium-labelling experiments and calculations which indicate that the two added hydrogen atoms of the products come from hydrogen gas. Additionally, it is believed that the reaction involves a Ni-II rather than Ni-0 cyclic process based on the weak attractive interactions between the Ni catalyst and terminal olefin substrate.

Automated summary

In this study, an efficient earth-abundant transition-metal nickel catalyzed asymmetric hydrogenation of chiral ethylphosphine products was reported. The products were obtained with up to 99% yield, 96% ee (enantiomeric excess) (99% ee, after recrystallization) and 1000 S/C (substrate/catalyst) ratio. This is also the first study on the asymmetric hydrogenation of terminal olefins using a nickel catalyst under a hydrogen atmosphere. Deuterium-labelling experiments and calculations revealed that the two added hydrogen atoms in the products came from hydrogen gas. Additionally, it was suggested that the reaction involves a Ni-II rather than Ni-0 cyclic process based on the weak attractive interactions between the Ni catalyst and terminal olefin substrate.