Cobalt-Catalyzed Enantioselective Hydroamination of Arylalkenes with Secondary Amines.

Angew Chem Int Ed Engl

Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, 130024, Changchun, China.

Published: January 2023

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 S 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.

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Source
http://dx.doi.org/10.1002/anie.202213913DOI Listing

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