Zn-ProPhenol Catalyzed Enantioselective Mannich Reaction of 2H-Azirines with Alkynyl Ketones

2020/12/03 by Barry M. Trost, Chuanle Zhu · 1 citation
Chemistry · #Synthesis and Catalytic Reactions #Catalytic C–H Functionalization Methods #Asymmetric Synthesis and Catalysis

paper · doi:10.1021/acs.orglett.0c03737

openalex publication_date 2020/12/03 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

-azirines with alkynyl ketones is achieved under Zn-ProPhenol catalysis, delivering various aziridines with vicinal tetrasubstituted stereocenters in high yields with excellent enantioselectivities. The bimetallic Zn-ProPhenol complexes activate both the nucleophile and the electrophile in the same chiral pocket. A unique intramolecular hydrogen bond is observed in the obtained Mannich adducts, which lowers the basicity of the product's aziridine nitrogen thus favoring enantioselective control and allowing catalyst turnover.

Citations

• Direct Catalytic Asymmetric Vinylogous Additions of α,β‐ and β,γ‐Butenolides to Polyfluorinated Alkynyl Ketimines
• Copper-Catalyzed Asymmetric Addition of Tertiary Carbon Nucleophiles to 2H-Azirines: Access to Chiral Aziridines with Vicinal Tetrasubstituted Stereocenters
• Copper(I)-catalyzed asymmetric decarboxylative Mannich reaction enabled by acidic activation of 2H-azirines

Cited by

• Ketimine Mannich reaction [wikipedia]

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