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Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2020-01-21 , DOI: 10.1002/anie.201912991
Lars Longwitz 1 , Thomas Werner 1
Affiliation  

The carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl‐substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.

中文翻译:

PIII / PV氧化还原循环催化还原活化的烯烃

在简单的有机硅烷作为末端还原剂和水作为氢源的情况下,使用氧化膦催化剂可以轻松地还原不饱和羰基化合物的碳-碳双键。当使用1.0 mol%的甲基取代的氧化膦作为催化剂时,可以观察到定量氢化。该方法对活化的双键具有高度选择性,可以耐受通常易于还原的各种官能团。总共将25个烯烃和两个炔烃氢化成相应的烷烃,产率高达99%。值得注意的是,活性较低的聚(甲基氢硅氧烷)也可以用作末端还原剂。
更新日期:2020-01-22
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