Dynamic Asymmetric Diamination of Allylic Alcohols through Borrowing Hydrogen Catalysis: Diastereo-divergent Synthesis of Tetrahydrobenzodiazepines.
Angew Chem Int Ed Engl
; : e202410351, 2024 Sep 21.
Article
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| ID: mdl-39305276
ABSTRACT
We present herein an unprecedented, catalytic enantioconvergent diamination of racemic allylic alcohols with the construction of two C-N bonds and 1,3-nonadjacent stereocenters. This iridium/chiral phosphoric acid cooperative catalytic system operates through an atom-economical borrowing hydrogen amination/aza-Michael cascade, and converts readily available phenylenediamines and racemic allylic alcohols to 1,5-tetrahydrobenzodiazepines in high enantioselectivity. An intriguing solvent-dependent switch of diastereoselectivity was also observed. Mechanistic studies suggested a dynamic kinetic resolution process involving racemization through a reversible Michael addition, making the last step of asymmetric imine reduction the enantiodetermining step of this cascade process.
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Bases de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2024
Tipo del documento:
Article
País de afiliación:
Singapur