Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling.
Organocatalytic Chlorination of Alcohols by P(III)/P(V) Redox Cycling.
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DOI：
10.1021/acs.joc.9b00741
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发表时间：
2019-05
期刊：
影响因子：
--
通讯作者：
Lars Longwitz;S. Jopp;T. Werner
中科院分区：
文献类型：
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作者：
Lars Longwitz;S. Jopp;T. Werner
在阿佩尔反应条件下，建立了醇类氯化反应的催化体系.苯并咪唑是一种廉价易得的氯化剂，与三辛基膦作为催化剂和苯基硅烷作为末端还原剂组合使用。该反应具有优于阿佩尔反应的其它变体的几个优点，例如，不需要额外的溶剂，并且膦试剂仅以催化量使用。总共合成了27种不同的伯、仲和叔烷基氯化物，产率高达95%。在优化的条件下，也可以将环氧化物和氧杂环丁烷转化为二氯化产物。
A catalytic system for the chlorination of alcohols under Appel conditions was developed. Benzotrichloride is used as a cheap and readily available chlorinating agent in combination with trioctylphosphane as the catalyst and phenylsilane as the terminal reductant. The reaction has several advantages over other variants of the Appel reaction, e.g., no additional solvent is required and the phosphane reagent is used only in catalytic amounts. In total, 27 different primary, secondary, and tertiary alkyl chlorides were synthesized in yields up to 95%. Under optimized conditions, it was also possible to convert epoxides and an oxetane to the dichlorinated products.