Mechanistic study of homoleptic trisamidolanthanide-catalyzed aldehyde and ketone hydroboration. Chemically non-innocent ligand participation† † Electronic supplementary information (ESI) available: Synthetic procedures, NMR spectra, X-ray crystallographic data, and computational details. CCDC 2196153, 2196157, and 2196158. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d2sc06442a.

ABSTRACT: Carbonyl bond hydroboration is a valuable synthetic route to functionalized alcohols but relies on sometimes unselective and sluggish reagents. While rapid and selective aldehyde and ketone hydroboration mediated by trisamidolanthanide catalysts is known, the origin of the selectivity is not well-understood and is the subject of this contribution. Here the aldehyde and ketone HBpin hydroboration reaction mechanisms catalyzed by La[N(SiMe3)2]3 are investigated both experimentally and theoretically. The results support initial carbonyl oxygen coordination to the acidic La center, followed by intramolecular ligand-assisted hydroboration of the carbonyl moiety by bound HBpin. Interestingly, ketone hydroboration has a higher energetic barrier than that of aldehydes due to the increased steric e

SUBMITTER: Rothbaum J 

PROVIDER: S-EPMC10034223 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature