Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

Abstract

Abstract:The catalytic synthesis of cyclic carbonates using carbon dioxide as a C1-building block is a highly active area of research. Here, we review the catalytic production of enantiomerically enriched cyclic carbonates via kinetic resolution of racemic epoxides catalysed by metal-containing catalyst systems.

Recent progress in stereoselective synthesis of cyclic organic carbonates and beyond

“…In other recent contributions, optically active cyclic carbonates were prepared by catalytic kinetic resolution of racemic epoxides in the presence of CO2 [21], with preferred activation of one of the two enantiomers of the (rac) epoxide. After initial attempts reported by Dibenedetto and Aresta [22] giving rather low ee (22%), important advances have been published over the last years.…”

“…After initial attempts reported by Dibenedetto and Aresta [22] giving rather low ee (22%), important advances have been published over the last years. Most of these focused on the use of metallosalen complexes, and Co-based systems have shown exceptional potential for the kinetic resolution of (rac) epoxides to afford chiral COCs [13,21].…”

Enantioselective “organocatalysis in disguise” by the ligand sphere of chiral metal-templated complexes

“…It should be emphasized, the kinetic resolution of epoxides with CO 2 is very challenging process and there are only few examples in literature where high s-factors were achieved. [173][174][175][176][177]…”

Kinetic Resolution of Epoxides with CO2 Catalyzed by a Chiral‐at‐Iridium Complex

“…[1,2] Although many efficient catalysts are known for the racemic reaction, [1] the kinetic resolution of racemic epoxides poses significant challenges (Scheme 1a). [3] Typically,t he selectivity factor s,w hich is defined as the ratio of the rate constants (k R and k S )f or the reactionw ith the two individual enantiomers (s = k R /k S ), is low( s < 10) for the reactiono fC O 2 with monosubstituted epoxides and no general catalytic system foravariety of different epoxide substrates is known. Chiral cobalt Schiff-base catalysts are the most studied and most successful catalysts to date.…”