Transition-metal catalysts play an important role in developing useful transformations of carbon dioxide (CO2), especially in C–C bond forming reactions.1 We found that regiodivergent silacarboxylation of allenes proceeded under CO2 atmosphere with PhMe2Si–B(pin) as a silicon source in the presence of a copper catalyst at 70 °C. The regioselectivity of the reaction is reversed by the proper choice of ligand; carboxylated vinylsilanes are obtained with rac-Me-DuPhos as the ligand, whereas carboxylated allylsilanes are provided by employing PCy3. 2 Furthermore, cobalt-catalyzed carboxyzincation reactions employing CO2 and Zn metal powder are developed. By using alkynes as substrates, regio- and stereodefined (Z)-b-zincated acrylates are provided via carboxyzincation.3 The resulting alkenylzinc moiety can be converted to afford various multi-substituted acrylic acids. By adding electron-deficient alkene to the reaction system, the four-component coupling reactions of alkyne, alkene, CO2, and the Zn proceed.3

Transition-metal-catalyzed functionalization using carbon dioxide

253rd National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.