Affiliation:
1. Department of Chemistry Northwestern University 2145 Sheridan Road Evanston Illinois 60208 USA
2. Department of Material Science and Engineering Northwestern University 2145 Sheridan Road Evanston Illinois 60208 USA
Abstract
AbstractEfficient hydroboration of aldehydes and ketones is demonstrated using a single‐site MoO2 catalyst supported on activated carbon. Under mild conditions with low catalytic loadings, the reaction exhibits chemoselectivity towards carbonyl reduction over halides, alkene, alkyne, nitrile, and ester groups, affording high yields of desired products. Furthermore, competition studies between aldehyde and ketone reduction using HBpin and HBcat indicate that HBpin preferably functionalizes aldehydes, while HBcat can functionalize either substrate under specific conditions. Mechanistic studies suggest that the reaction proceeds via the initial formation of a molybdenum‐hydride species upon B−H activation and subsequent molybdenum‐alkoxide species upon carbonyl activation by the Mo center. The experimental activation energy of 14.3 kcal/mol alignssatisfactorily with the DFT computed ΔH≠ of 18.7 kcal/mol, further supporting the proposed mechanism. Combined experimental/computational analyses reveal that excess HBpin can possibly deactivate the catalyst. The presence of excess benzaldehyde efficiently mitigates deactivation by HBpin, providing significantly higher catalyst recyclability. Overall, this non‐toxic, air‐ and moisture‐stable, active, and selective catalyst demonstrates significant potential for green processes.
Subject
Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis