Selective Oxytrifluoromethylation of Allylamines with CO₂

Abstract

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.

Synthesis of Oxazolidin‐2‐ones from Unsaturated Amines with CO2 by Using Homogeneous Catalysis

“…In 2016, Yu′s group reported an oxytrifluoromethylation of allylamines with CO 2 promoted by copper catalysis, thereby affording important CF 3 ‐containing 2‐oxazolidones with high chemoselectivity, regioselectivity, and diastereoselectivity (Scheme ) . This multicomponent reaction featured broad substrate scope, good functional‐group tolerance, and facile scalability.…”

Radical‐Mediated Non‐Dearomative Strategies in Construction of Spiro Compounds

“…In consideration of this, Yu group reported oxytrifluoromethylation of allylamines 112 with CO 2 using copper-catalyzed process in synthesis of CF 3 -containig spiro 2-oxazolidinones 113 (Scheme 31). [50] Presented concept serves as an excellent example of chemo-regio-and diastereoselective radical spirocyclization, with multiple bond formation and multiple functional group incorporation.…”

In situ tether formation from amines and alcohols enabling highly selective Tsuji–Trost allylation and olefin functionalization

“… 21 Recently Yu and coworkers disclosed a Cu-catalyzed oxy-trifluoromethylation of allylamines using CO 2 gas to form the tether, in which one C–O and one C–C bonds are formed ( Scheme 10 ). 22 The combination of a nucleophilic allylic amine, CO 2 and Togni's reagent 29 in presence of a copper catalyst and a base led to the oxy-trifluoromethylation of the olefin in high yield and diastereoselectivity. Notably, the developed reaction allowed for mild conditions with CO 2 at atmospheric pressure.…”