Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers |
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| Authors: | Wentao Xu Junyang Ma Prof?Dr Xiang‐Ai Yuan Dr Jie Dai Prof?Dr Jin Xie Prof?Dr Chengjian Zhu |
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| Institution: | 1. http://hysz.nju.edu.cn/xie/;2. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, National Demonstration Center for Experimental Chemistry, Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, P. R. China;3. School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, P. R. China;4. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, P. R. China |
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| Abstract: | 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. |
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| Keywords: | C− O bond activation cooperative catalysis polarity-matching effect trifluoromethylthiolation umpolung |
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