Catalytic C–H Carboxylation of Terminal Alkynes with Carbon Dioxide

Abstract

Within the past years, several catalyst systems have been discovered that promote the carboxylation of terminal alkynes with formation of propiolic acids. This reaction concept is particularly topical in that it involves the functionalization of a C–H bond and the incorporation of CO2 into an organic molecule without need for strong bases or aggressive organometallic reagents. The present article reviews the development of this new reaction type and critically compares the reaction and catalyst concepts disclosed in the literature.

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

“…These observations suggest that strong coordination between the electron-rich metal center and ligand activates the CO 2 Terminal alkynes display relatively acidic C-H bonds (pK a * 25) and can undergo carboxylation at elevated temperatures and pressures [40,41]. In the presence of a catalyst [58], mild carboxylations have been reported with copper and silver salts, both with [59][60][61] and without [62][63][64][65] external halide reagents to trap the formed carboxylate ( Fig. 6).…”

Transition Metal-Catalyzed Carboxylation of Organic Substrates with Carbon Dioxide

“…Since this report, several contributions have significantly improved on this useful reaction. Recently, the results in this area have been highlighted by Gooßen [83]. These and other rapid developments in copper-based catalysis opened new perspectives for reaction methodologies involving the catalytic CO 2 incorporation by copper complexes in organic synthesis (Fig.…”

Using sustainable metals to carry out “green” transformations: Fe- and Cu-catalyzed CO2 monetization

“…During the 70's, a series of pioneering publications on the catalytic transformation of CO 2 to formic acid and its derivatives was reported by the research groups of Inoue, Sobota, and Vol'pin [12][13][14][15]. Since then, numerous transition metal complexes have been synthesized and evaluated as catalysts in a variety of homogeneous CO 2 catalytic transformations [4,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. However, in most cases, rare, A c c e p t e d M a n u s c r i p t Edited Jan 21…”