Nickel‐Catalyzed Enantioselective Direct Addition of 1,3‐Dienes to Aldehydes Enabled by Chiral Monodentate Diamidophosphite Ligands

ABSTRACT Enantioenriched dienols are important structural motifs in numerous bioactive compounds and serve as valuable intermediates in organic synthesis. Although several synthetic routes have been developed, the most desirable approach is the direct addition of 1,3‐dienes to aldehydes, thereby avoiding the need for preformed alkenylmetal reagents. Herein, we report the first enantioselective direct addition of 1,3‐dienes to aldehydes, enabled by nickel(0) catalysis in combination with a newly developed class of chiral monodentate diamidophosphite ligands derived from chiral 1,2‐diamine scaffolds. This method affords chiral dienols in high yields and with excellent regio‐ and enantioselectivity under mild, redox‐neutral, and atom‐economical conditions. Comprehensive mechanistic studies—including both experimental investigations and DFT calculations—reveal a catalytic cycle involving oxo‐nickelacycle intermediates. The high selectivity arises from the chiral diamidophosphite ligands, which provide precise stereocontrol by stabilizing key intermediates through noncovalent CH···HC interactions.