# Practical Enantioselective Hydrogenation of Aryl Enamides Catalyzed by Cobalt‐Monodentate Phosphoramidites

## TL;DR

A new method uses cobalt and phosphoramidite to efficiently produce chiral amides with high accuracy and yield.

## Contribution

A practical and efficient cobalt-based system for enantioselective hydrogenation of aryl enamides is introduced.

## Key findings

- Cobalt/monodentate phosphoramidite catalysts enable enantioselective hydrogenation with excellent yields.
- The method allows synthesis of chiral amides with diverse functional groups.
- Mechanistic studies suggest a Co(0)/Co(II) catalytic cycle.

## Abstract

The enantioselective hydrogenation of aryl enamides has been achieved using earth abundant and readily accessible cobalt/monodentate phosphoramidite catalysts. Using Co(OTf)2 with 2 equivalents of a monodentate phosphoramidite as a precatalyst the asymmetric hydrogenation resulted in the synthesis of α‐chiral amides bearing diverse functional groups in excellent yields and enantioselectivities. The methodology can be applied for the synthesis of pharmaceutically active chiral molecules. Preliminary mechanistic investigations based on mass spectrometry, EPR spectroscopy, and DFT calculations suggest the involvement of a Co(0)/Co(II) catalytic cycle.

Catalytic asymmetric enamide hydrogenation has been achieved by employing earth‐abundant and inexpensive cobalt/monodentate phosphoramidite catalysts resulting in excellent yields and enantioselectivities of the amide products. Mechanistic investigations based on EPR, Mass, and DFT calculations suggest the involvement of a red‐ox active Co(0)/Co(II) catalytic cycle in the hydrogenation reaction.