Aldehyde and Ketone Hydroboration Mediated by a Heterogeneous Single–Site Molybdenum–Dioxo Catalyst: Scope and Mechanistic Implications

Liu, Yiqi; Agarwal, Amol; Ye, Liwei; Kratish, Yosi; Marks, Tobin J.

doi:10.1002/cctc.202301417

Aldehyde and Ketone Hydroboration Mediated by a Heterogeneous Single–Site Molybdenum–Dioxo Catalyst: Scope and Mechanistic Implications

Journal Article · Wed Dec 20 00:00:00 EST 2023 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.202301417· OSTI ID:2480924

Liu, Yiqi ^[1]; Agarwal, Amol ^[1]; Ye, Liwei ^[1]; Kratish, Yosi ^[1]; ^[1]

Northwestern University, Evanston, IL (United States)

Efficient 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. Altogether, this non-toxic, air- and moisture-stable, active, and selective catalyst demonstrates significant potential for green processes.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: NASA Ames Research Center; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15457; SC0024448

OSTI ID:: 2480924

Alternate ID(s):: OSTI ID: 2335843
OSTI ID: 2571098

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 7 Vol. 16; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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08 HYDROGEN
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hydroboration
mechanistic studies
molybdenum
single-site catalysts

Aldehyde and Ketone Hydroboration Mediated by a Heterogeneous Single–Site Molybdenum–Dioxo Catalyst: Scope and Mechanistic Implications

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