Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities
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',2"-terpyridine ligand (Rtpy•)– 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 ~1000 and turnover frequencies (TOFs) of up to ~500 h–1. In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.
- Authors:
-
[1];
[3];
[3];
[4];
[5];
[5];
[6]
- The Graduate Center of City Univ. of New York, New York, NY (United States)
- The Graduate Center of City Univ. of New York, New York, NY (United States); City Univ. of New York, New York, NY (United States)
- City Univ. of New York, New York, NY (United States)
- Southwest Petroleum Univ., Sichuan (People’s Republic of China)
- Arizona State Univ., Tempe, AZ (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1570623
- Report Number(s):
- LA-UR-19-22935
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 38; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry; Organic Chemistry
Citation Formats
Zhang, Guoqi, Wu, Jing, Zheng, Shengping, Neary, Michelle C., Mao, Jincheng, Flores, Marco, Trovitch, Ryan J., and Dub, Pavel A. Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b07062.
Zhang, Guoqi, Wu, Jing, Zheng, Shengping, Neary, Michelle C., Mao, Jincheng, Flores, Marco, Trovitch, Ryan J., & Dub, Pavel A. Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities. United States. https://doi.org/10.1021/jacs.9b07062
Zhang, Guoqi, Wu, Jing, Zheng, Shengping, Neary, Michelle C., Mao, Jincheng, Flores, Marco, Trovitch, Ryan J., and Dub, Pavel A. Tue .
"Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities". United States. https://doi.org/10.1021/jacs.9b07062. https://www.osti.gov/servlets/purl/1570623.
@article{osti_1570623,
title = {Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities},
author = {Zhang, Guoqi and Wu, Jing and Zheng, Shengping and Neary, Michelle C. and Mao, Jincheng and Flores, Marco and Trovitch, Ryan J. and Dub, Pavel A.},
abstractNote = {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',2"-terpyridine ligand (Rtpy•)– 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 ~1000 and turnover frequencies (TOFs) of up to ~500 h–1. In conclusion, computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.},
doi = {10.1021/jacs.9b07062},
journal = {Journal of the American Chemical Society},
number = 38,
volume = 141,
place = {United States},
year = {2019},
month = {9}
}
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