Efficient Difluoromethylation of Alcohols Using TMSCF2Br as a Unique and Practical Difluorocarbene Reagent under Mild Conditions,Angewandte Chemie International Edition

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Efficient Difluoromethylation of Alcohols Using TMSCF2Br as a Unique and Practical Difluorocarbene Reagent under Mild Conditions
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2017-02-09 , DOI: 10.1002/anie.201611823
Qiqiang Xie ₁ , Chuanfa Ni ₁ , Rongyi Zhang _{1,

2} , Lingchun Li ₁ , Jian Rong ₁ , Jinbo Hu _{1,

2}

Affiliation

A general method for the efficient difluoromethylation of alcohols using commercially available TMSCF₂Br (TMS=trimethylsilyl) as a unique and practical difluorocarbene source is developed. This method allows primary, secondary, and even tertiary alkyl difluoromethyl ethers to be synthesized under weakly basic or acidic conditions. The reaction mainly proceeds through the direct interaction between a neutral alcohol and difluorocarbene, which is different from the difluoromethylation of phenols. Moreover, alcohols containing other moieties that are also reactive toward difluorocarbene can be transformed divergently by using TMSCF₂Br. This research not only solves the synthetic problem of difluorocarbene‐mediated difluoromethylation of alcohols, it also provides new insights into the different reaction mechanisms of alcohol difluoromethylation and phenol difluoromethylation with difluorocarbene species.

中文翻译：

在温和条件下使用TMSCF2Br作为独特而实用的二氟卡宾试剂对醇进行有效的二氟甲基化

开发了一种使用市售TMSCF ₂ Br（TMS =三甲基甲硅烷基）作为独特实用的二氟卡宾源的有效二氟甲基化醇的通用方法。该方法允许在弱碱性或酸性条件下合成伯，仲，甚至叔烷基二氟甲基醚。该反应主要通过中性醇与二氟卡宾之间的直接相互作用而进行，这与酚的二氟甲基化不同。此外，通过使用TMSCF ₂可以发散地转化含有对二氟卡宾也具有反应性的其他部分的醇。br。这项研究不仅解决了二氟卡宾介导的醇二氟甲基化的合成问题，而且为了解醇二氟甲基化和苯酚二氟甲基化与二氟卡宾物种的不同反应机理提供了新见解。

更新日期：2017-02-09

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