期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 57, 期 32, 页码 10357-10361出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201805927
关键词
C-O bond activation; cooperative catalysis; polarity-matching effect; trifluoromethylthiolation; umpolung
资金
- National Natural Science Foundation of China [21702098, 21732003, 21672099, 21703118]
- 1000-Youth Talents Plan
- Fundamental Research Funds for the Central Universities [020514380158, 020514380131]
- Shandong Provincial Natural Science Foundation [ZR2017MB038]
- open training program of undergraduate organic experiment course
The first transition-metal-free, site-specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp(3))-SCF3 coupling under redox-neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL-based phosphorothiols can site-selectively cleave tertiary sp(3) C(sp(3))-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(sp(3))-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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