Cross-Selective Aza-Pinacol Coupling via Atom Transfer Catalysis.
J Am Chem Soc
; 143(15): 5622-5628, 2021 04 21.
Article
in En
| MEDLINE
| ID: mdl-33830738
ABSTRACT
A cross-selective aza-pinacol coupling of aldehydes and imines has been developed to afford valuable ß-amino alcohols. This strategy enables chemoselective conversion of aliphatic aldehydes to ketyl radicals, in the presence of more easily reduced imines and other functional groups. Upon carbonyl-specific activation by AcI, a photoinitiated Mn catalyst selectively reduces the resulting α-oxy iodide by an atom transfer mechanism. The ensuing ketyl radical selectively couples to imines, precluding homodimerization by a classical reductive approach. In this first example of reductive, ketyl coupling by atom transfer catalysis, Zn serves as a terminal reductant to facilitate Mn catalyst turnover. This new strategy also enables ketyl radical couplings to alkenes, alkynes, aldehydes, propellanes, and chiral imines.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Oligopeptides
/
Aza Compounds
Language:
En
Journal:
J Am Chem Soc
Year:
2021
Document type:
Article
Affiliation country:
United States