Cobalt-Catalyzed Enantioselective Hydroamination of Arylalkenes with Secondary Amines.
Angew Chem Int Ed Engl
; 62(2): e202213913, 2023 01 09.
Article
in En
| MEDLINE
| ID: mdl-36342476
ABSTRACT
Catalytic asymmetric hydroamination of alkenes with Lewis basic amines is of great interest but remains a challenge in synthetic chemistry. Here, we developed a Co-catalyzed asymmetric hydroamination of arylalkenes directly using commercially accessible secondary amines. This process enables the efficient access to valuable α-chiral tertiary amines in good to excellent yields and enantioselectivities. Mechanistic studies suggest that the reaction includes a CoH-mediated hydrogen atom transfer (MHAT) with arylalkenes, followed by a pivotal catalyst controlled SN 2-like pathway between in situ generated electrophilic cationic alkylcobalt(IV) species and free amines. This radical-polar crossover strategy not only provides a straightforward and alternative approach for the synthesis of enantioenriched α-tertiary amines, but also underpins the substantial opportunities in developing asymmetric radical functionalization of alkenes with various free nucleophiles in oxidative MHAT catalysis.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Cobalt
/
Amines
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2023
Type:
Article
Affiliation country:
China