Enantioselective Trifluoromethylthiolating Lactonization Catalyzed by an Indane-Based Chiral Sulfide

• Published in: Angewandte Chemie International Edition Vol. 55; no. 19; pp. 5846 - 5850
• Main Authors: Liu, Xiang, An, Rui, Zhang, Xuelin, Luo, Jie, Zhao, Xiaodan
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 04.05.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkenes; asymmetric catalysis; Chemistry; Chemistry, Multidisciplinary; chiral sulfides; organocatalysis; Physical Sciences; Science & Technology; Sulfides; Sulfur; trifluoromethylthiolation; HYPERVALENT IODONIUM YLIDE; OXIDATIVE TRIFLUOROMETHYLTHIOLATION; INTRAMOLECULAR CARBOSULFENYLATION; ELECTROPHILIC TRIFLUOROMETHYLTHIOLATION; asymmetric catalysis; alkenes; trifluoromethylthiolation; C-H BONDS; UNACTIVATED ALKENES; organocatalysis; MEDICINAL CHEMISTRY; BORONIC ACIDS; chiral sulfides; ALPHA-FLUORINATED ETHERS; SILVER(I) TRIFLUOROMETHANETHIOLATE
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201601713

Enantioselective trifluoromethylthiolation, especially of alkenes, is a challenging task. In this work, we have developed an efficient approach for enantioselective trifluoromethylthiolating lactonization by designing an indane‐based bifunctional chiral sulfide catalyst and a shelf‐stable electrophilic SCF3 reagent. The desired products were formed with diastereoselectivities of >99:1 and good to excellent enantioselectivities. The transformation represents the first enantioselective trifluoromethylthiolation of alkenes and the first enantioselective trifluoromethylthiolation that is enabled by a catalyst with a Lewis basic sulfur center. An efficient approach for enantioselective trifluoromethylthiolating lactonization entails the use of an indane‐based bifunctional chiral sulfide catalyst and a new shelf‐stable electrophilic SCF3 reagent. This transformation represents the first enantioselective trifluoromethylthiolation that is enabled by a catalyst with a Lewis basic sulfur center.