Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers,Angewandte Chemie International Edition

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Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-12 , DOI: 10.1002/anie.201805927
Wentao Xu ₁ , Junyang Ma ₁ , Xiang-Ai Yuan ₂ , Jie Dai ₁ , Jin Xie ₁ , Chengjian Zhu _{1,

3}

Affiliation

The first transition‐metal‐free, site‐specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp³)–SCF₃ coupling under redox‐neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL‐based phosphorothiols can site‐selectively cleave tertiary sp³ C(sp³)–O ether bonds in complex molecules initiated by a polarity‐matching hydrogen‐atom‐transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp³)−H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C−O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site‐selective C−O bond functionalization of unsymmetrical tertiary alkyl ethers.

中文翻译：

协同催化叔醚三氟甲基硫醇化

已经开发出第一个无过渡金属，特定位点的叔烷基醚的三氟甲基硫代三氟甲基硫醇化反应，实现了在氧化还原-中性条件下具有挑战性的叔C（sp ³）-SCF ₃偶联。有机光催化剂4CzIPN和基于BINOL的硫代硫醇的协同作用可以在极性匹配的氢原子转移（HAT）事件引发的复杂分子中选择性地裂解叔sp ³ C（sp ³）-O醚键。几个竞争性苄基和次甲基C（sp ³的合并烷基醚中的）-H键对区域选择性影响很小。还已经实现了对CO键的选择性二氟甲基硫醇化。这不仅代表了三氟甲基硫醇化的重要一步，而且是不对称叔烷基醚的位点选择性C-O键功能化的一种有前途的手段。

更新日期：2018-07-12

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