Correction to “Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C═X (X = O, N) Functionalities”
Correction to “Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C═X (X = O, N) Functionalities”
复制标题
对“氧化还原非无害配体支持的钒催化剂用于化学选择性还原 C”X (X = O, N) 功能性的修正
DOI：
10.1021/jacs.0c09331
复制
发表时间：
2020
影响因子：
15
通讯作者：
Dub, Pavel A.
中科院分区：
文献类型：
--
作者：
Zhang, Guoqi;Wu, Jing;Zheng, Shengping;Neary, Michelle C.;Mao, Jincheng;Flores, Marco;Trovitch, Ryan J.;Dub, Pavel A.
催化是钒的第二大应用，仅次于用作提高钢铁产量的添加剂。钒（V）的分子络合物是氧化过程中特别有用和有效的催化剂;然而，它们催化还原转化的能力尚未得到充分研究。在这里，我们报告了第一个由V介导的极性有机官能团还原的例子。开壳层VIII配合物的特征是在4′-位官能化的π-自由基单阴离子2，2 ′：6′，2 ″-三联吡啶配体（Rtpy·）−（R =（CH 3）3SiCH 2，C6 H5）催化官能化的酮、醛、亚胺、酯和羧酰胺的温和的化学选择性硼氢化和硅氢化反应，其转换数（TON）高达1000，转换频率（TOF）高达1500 h-1。催化剂前体合成和活化的计算评价揭示了与氧化还原活性的tpy螯合物相关的未被充分认识的复杂性。
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 VIIIcomplexes 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. Computational evaluation of the precatalyst synthesis and activation has revealed underappreciated complexity associated with the redox-active tpy chelate.