Construction of C–Cu Bond: A Useful Strategy in CO₂ Conversion

Abstract

Carbon dioxide is not only one of the greenhouse gases but also an appealing renewable C 1 source. To reconcile the environmental benefit with chemical industry development, conversion of CO 2 into valuable chemicals is proposed, and tremendous effort has been devoted to developing new synthetic protocols and highly efficient catalytic systems, wherein copper catalysis is attractive and features effective, inexpensive, and diverse transformation of CO 2 . Considering the ubiquity of the C−Cu bond in organic chemistry and the wide application of the resulting carbocuprate species in reductive coupling with electrophiles, C−Cu formation and subsequent CO 2 insertion has been developed as an important strategy for CO 2 chemical fixation, thereby resulting in the preparation of a variety of valuable chemicals. To arouse broad interest in this strategy, we summarize recent advances and give an overview on CO 2 transformations via the carbocuprate species on the basis of the C−Cu bond formation mechanism, including copper-promoted alkyne and halide activation, transmetalation of some specific chemicals with copper, and hydrocupration, borocupration, and silylcupration of unsaturated substrates. It is hoped that this review can provide some clues for further exploration in this field.

Chemodivergent Synthesis of Oxazolidin-2-ones via Cu-Catalyzed Carboxyl Transfer Annulation of Propiolic Acids with Amines

“…Based on the above experimental results and related literature reports, we conclude that there are two plausible catalytic pathways for the synthesis of products 3 and 4 , respectively (Scheme ). On one hand, primary amine 1 is oxidized to form imine 3-A through a process of oxidative deamination of 1 in the presence of the copper catalyst and NBS .…”

Stereodivergent synthesis of β-iodoenol carbamates with CO2viaphotocatalysis

“…The development of new and efficient methodologies for the conversion of carbon dioxide (CO 2 ) into valuable chemicals is of great significance, because CO 2 is considered as an ideal C1 feedstock in organic synthesis. 1 Recently, visible-light photocatalysis has become a powerful strategy for CO 2 transformation and attracted ever-increasing attention from chemists. 2 Many elegant methods that cannot be achieved through conventional thermal catalysis have been successfully developed to produce various valued-added chemicals and fuels from CO 2 , such as CO, 3 CH 3 OH, 4 CH 4 (ref.…”

Synthesis of carbonates from CO2 and epoxides catalyzed by the system of N‐heterocyclic carbene, hydrogen bond donor, CrCl2, and tetrabutylammonium bromide

“…To date, a number of methods for utilizing CO 2 have been developed. [ 2 ] The synthesis of cyclic carbonates via the fixation of CO 2 have witnessed a significant development in recent years due to the transformation possessing the features of high atomic economy. [ 3 ] It is well known that CO 2 was the thermodynamically inert and highly kinetically stable molecular; thus, high temperature and high pressure for CO 2 in the synthesis of cyclic carbonates is often required.…”