Copper-Catalyzed Divergent Trifluoromethylation/Cyclization of Unactivated Alkenes

• Published in: Advanced synthesis & catalysis Vol. 358; no. 5; pp. 746 - 751
• Main Authors: Zheng, Jing, Deng, Ziyang, Zhang, Yan, Cui, Sunliang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.03.2016; WILEY‐VCH Verlag; Wiley
• Subjects: Alkenes; Bonding; Catalysis; Chemistry; Chemistry, Applied; Chemistry, Organic; divergent synthesis; heterocycles; Isotope effect; Organic chemistry; Physical Sciences; Radicals; Science & Technology; Synthesis; Terminals; trifluoromethylation; unactivated alkenes; radicals; ARENES; BOND FORMATION; unactivated alkenes; REDUCTIVE ELIMINATION; divergent synthesis; FUNCTIONALIZATION; 3-COMPONENT OXYTRIFLUOROMETHYLATION; ARYLTRIFLUOROMETHYLATION; FACILE SYNTHESIS; heterocycles; FLUORINE; trifluoromethylation; DERIVATIVES; CYCLIZATION
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201500965

Most of the precedent copper‐catalyzed trifluoromethylation reactions of unactivated alkenes concern terminal alkenes, and these processes are terminated in elimination, or nucleophilic addition, or semipinacol rearrangement, or CH bond functionalization steps. In this study, we develop a trifluoromethylation method for both unactivated terminal and internal alkenes to enable divergent late‐stage radical cyclization and achieve high molecular complexity. These cyclizations are well consistent with Baldwin’s rule. Furthermore, a kinetic isotope effect (KIE) study and control reactions were conducted, and a plausible mechanism is proposed.