Issues of decreased carbon resources and sustainability have made the conversion of CO₂ into useful chemicals a hot topic in chemistry in recent years and a great amount of attention is currently being paid to this area. At the same time, transition-metal-mediated allylation reactions have emerged as a powerful method for the regio-, diastereo-, and enantioselective formation of carbon-carbon or carbon-heteroatom bonds.

X.-M. Zhao and co-workers, Tongji University, China, have combined these two important areas of chemical study by the proposition that CO₂ may be recycled by an attack of nucleophile such as an amine to induce an amidation reaction, which would then be followed by an Ir-catalyzed allylation reaction to give a branched allylic carbamate. Upon examining this proposition, the group achieved the enantioselective transformation of allyl carbonates into branched allyl carbamates by using amines and recycling CO₂ in the presence of an Ir-complex and K₃PO4. Products were produced in fair to excellent yields with excellent regio- (98:2) and enantioselectivity (93 % ee).

Allyl carbamates are an important class of compounds with broad interest with regards to both synthetic intermediates and biologically active molecules, therefore, a new synthetic method for their preparation is highly desirable.

• Enantioselective Transformation of Allyl Carbonates into Branched Allyl Carbamates by Using Amines and Recycling CO₂ under Iridium Catalysis,
  Sheng-Cai Zheng, Min Zhang, Xiao-Ming Zhao,
  Chem. Eur. J. 2014.
  DOI: 10.1002/chem.201402388