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Nickela-electrocatalyzed C-H Alkoxylation with Secondary Alcohols: Oxidation-Induced Reductive Elimination at Nickel(III).
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2020-01-16 , DOI: 10.1002/anie.201913930
Shou-Kun Zhang 1 , Julia Struwe 1 , Lianrui Hu 1 , Lutz Ackermann 1
Affiliation  

Nickela-electrooxidative C-H alkoxylations with challenging secondary alcohols were accomplished in a fully dehydrogenative fashion, thereby avoiding stoichiometric chemical oxidants, with H2 as the only stoichiometric byproduct. The nickela-electrocatalyzed oxygenation proved viable with various (hetero)arenes, including naturally occurring secondary alcohols, without racemization. Detailed mechanistic investigation, including DFT calculations and cyclovoltammetric studies of a well-defined C-H activated nickel(III) intermediate, suggest an oxidation-induced reductive elimination at nickel(III).

中文翻译:

镍电催化 CH 与仲醇的烷氧基化:镍 (III) 的氧化诱导还原消除。

镍电氧化CH烷氧基化与具有挑战性的仲醇以完全脱氢的方式完成,从而避免了化学计量的化学氧化剂,其中H2是唯一的化学计量副产物。事实证明,镍电催化氧化对于各种(杂)芳烃(包括天然存在的仲醇)是可行​​的,无需外消旋化。详细的机理研究,包括明确的 CH 活化镍 (III) 中间体的 DFT 计算和循环伏安研究,表明镍 (III) 存在氧化诱导的还原消除。
更新日期:2020-01-16
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