Kinetic Resolution Approach to the Synthesis of C-N Axially Chiral N-Aryl Aminomaleimides via NHC-Catalyzed [3 + 3] Annulation

Soumen Barik; Rohan Chandra Das; Kuruva Balanna; Akkattu T Biju

doi:10.1021/acs.orglett.2c02185

Kinetic Resolution Approach to the Synthesis of C-N Axially Chiral N-Aryl Aminomaleimides via NHC-Catalyzed [3 + 3] Annulation

Org Lett. 2022 Jul 29;24(29):5456-5461. doi: 10.1021/acs.orglett.2c02185. Epub 2022 Jul 20.

Authors

Soumen Barik¹, Rohan Chandra Das¹, Kuruva Balanna¹, Akkattu T Biju¹

Affiliation

¹ Department of Organic Chemistry, Indian Institute of Science, Bangalore-560012, India.

PMID: 35856856
DOI: 10.1021/acs.orglett.2c02185

Abstract

Chiral NHC-catalyzed kinetic resolution of N-aryl aminomaleimides allowing the synthesis of C-N axially chiral N-aryl aminomaleimides via remote chirality control is presented. The catalytically generated α,β-unsaturated acylazoliums from 2-bromoenals underwent selective [3 + 3] annulation with one of the enantiomers of maleimide to furnish fused-dihydropyridinone (bearing axial/central chirality, up to 6:1 dr, >99:1 er) leaving the enantioenriched opposite enantiomer (up to >99:1 er). Studies on C-N bond rotation barrier and dependence on temperature are also provided.