Carbon dioxide as renewable and environmentally friendly C1 carbon feedstock, which is in contrast to toxic CO and phosgene, has attracted increasing attention due to the cheap, abundant, and readily available carbon source. The formation of C-N and C-O bond is one of the most desirable forms of CO2 fixation. On the other hand, cyclic carbonates, oxazolidinones, and carbamates are of great interest due to their extensive application as useful intermediates in organic synthesis.We have developed Ag2WO4/Ph3P as an efficient and robust bifunctional catalytic system for chemical fixation of atmospheric CO2via the carboxylative cyclization of propargylic alcohols and CO2 or the three-component reaction of propargylic alcohols, amines and CO2 to produce valuable compounds. The present catalyst system worked well for a variety of propargylic alcohols, and particular for the three-component reaction of propargylic alcohols, primary amines or secondary amines and CO2. Strikingly, the catalytic system is not sensitive to minor moisture and air. Moreover, the reactions can be conducted under solvent-free conditions, rendering the strategy practical for recycling atmospheric CO2 into value-added a-alkylidene cyclic carbonates, a-alkylidene cyclic carbamates, and �-oxopropylcarbamates.In addition, bifunctional (nBu4N)3PO4-catalyzed system was established for constructing of a-alkylidene cyclic carbonate presumably through carboxylative cyclization of propargyl alcohols with CO2. In particular, nucleophilicity and basicity of the present catalyst would account for CO2 pressure required for performing the reaction smoothly, whereas suitable reaction temperature could be responsible for activation of C-C triple bond.

Bifunctional silver (I) catalysis for CO<sub>2</sub> upgrading

248th National Meeting (2014)

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Bifunctional silver (I) catalysis for CO2 upgrading

Bifunctional silver (I) catalysis for CO₂ upgrading