Iridium-Catalyzed Z-Retentive Asymmetric Allylic Substitution Reactions

Key words

iridium catalysis - enantioselectivity - Z-selectivity

Significance

The You group reports two unique methods for enantioselective iridium-catalyzed ­allylic substitution reactions, which are highly ­selective for the thermodynamically less stable Z-alkene products. Conventionally, metal-catalyzed asymmetric allylic substitution reactions favor the E-isomer of the products.

Comment

The authors rationalized their reaction design by focusing on developing a catalytic system that allowed for a slow isomerization from the initial anti-π-allyl complex to the more favored syn-π-allyl species. Subsequent capture of the chiral anti-π-iridium species by a nucleophile selectively generated the enantioenriched Z-alkene products.

Publication History

Article published online:
20 April 2021