Selective Oxytrifluoromethylation of Allylamines with CO2

• Published in: Angewandte Chemie (International ed.) Vol. 55; no. 34; pp. 10022 - 10026
• Main Authors: Ye, Jian-Heng, Song, Lei, Zhou, Wen-Jun, Ju, Tao, Yin, Zhu-Bao, Yan, Si-Shun, Zhang, Zhen, Li, Jing, Yu, Da-Gang
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 16.08.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Carbon dioxide; Chemistry; Chemistry, Multidisciplinary; copper; fluorine; heterocycles; Physical Sciences; reaction mechanisms; Science & Technology; carbon dioxide; ROOM-TEMPERATURE; ORGANIC-SYNTHESIS; reaction mechanisms; C-H BONDS; UNACTIVATED ALKENES; 3-COMPONENT OXYTRIFLUOROMETHYLATION; COPPER-CATALYZED TRIFLUOROMETHYLATION; heterocycles; ALLYLIC ALCOHOLS; copper; RECENT PROGRESS; CARBON-DIOXIDE; ELECTROPHILIC TRIFLUOROMETHYLATION; fluorine
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201603352

Reported is the first oxy‐trifluoromethylation of allylamines with carbon dioxide (CO2) using copper catalysis, thus leading to important CF3‐containing 2‐oxazolidones. It is also the first time CO2, a nontoxic and easily available greenhouse gas, has been used to tune the difunctionalization of alkenes from amino‐ to oxy‐trifluoromethylation. Of particular note, this multicomponent reaction is highly chemo‐, regio‐, and diastereoselective under redox‐neutral and mild reaction conditions. Moreover, these reactions feature good functional‐group tolerance, broad substrate scope, easy scalability and facile product diversification. The important products could also be formed with either spirocycles or two adjacent tetrasubstituted carbon centers. CO2 changes things: The title reaction leads to important 2‐oxazolidones. CO2 plays a vital role in tuning the difunctionalization of alkenes from amino‐ to oxytrifluoromethylation. This reaction is highly chemo‐, regio‐, and diastereoselective under redox‐neutral and mild reaction conditions. Moreover, these reactions feature good functional‐group tolerance, broad substrate scope, and easy scalability.