Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of CâX (X = O, N) Functionalities.
J Am Chem Soc
; 141(38): 15230-15239, 2019 09 25.
Article
em En
| MEDLINE
| ID: mdl-31479257
ABSTRACT
Catalysis is the second largest application for V after its use as an additive to improve steel production. Molecular complexes of vanadium(V) are particularly useful and efficient catalysts for oxidation processes; however, their ability to catalyze reductive transformations has yet to be fully explored. Here we report the first examples of polar organic functionality reduction mediated by V. Open-shell VIII complexes that feature a π-radical monoanionic 2,2'6',2â³-terpyridine ligand (Rtpyâ¢)- functionalized at the 4'-position (R = (CH3)3SiCH2, C6H5) catalyze mild and chemoselective hydroboration and hydrosilylation of functionalized ketones, aldehydes, imines, esters, and carboxamides with turnover numbers (TONs) of up to â¼1000 and turnover frequencies (TOFs) of up to â¼500 h-1. Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.
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MEDLINE
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En
Ano de publicação:
2019
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Article