N-heterocyclic carbene (NHC) supported Cu complexes catalyze carboxylation of organoboronic esters. The catalyst forms in situ from CuCl, an NHC ligand, and KOBu. Copper tert-butoxide can transmetallate with the organoboronic ester to generate the Cu-C bond, which intermediate can insert into CO smoothly to get the respective carboxylate. Salt metathesis with KOBu releases product and regenerates catalyst (Scheme 2).
 Apart from transmetallation, there are other approaches forming Cu-C bond. C-H functionalization is a straightforward and atom economic method. Base can help deprotonate acidic C-H protons and form Cu-C bond. [(Phenanthroline)Cu(PR)] catalyst effect C-H carboxylation on terminal alkynes together with CsCO. NHC-Cu-H species to deprotonate acidic proton to effect carboxylation of terminal alkynes. Cu-H species were generated from Cu-F and organosilanes. The carboxylate product was trapped by silyl fluoride to get silyl ether. For non-acidic C-H bonds, directed metalation with BuAl(TMP)Li is adopted followed by transmetallation with copper to get Cu-C bond. Allylic C-H bonds and phenyl C-H bonds got carboxylated with this approach by Hou and co-workers:
 Carbometallation to alkynes and allenes using organozinc and organoaluminum reagents followed by transmetallation to copper is also a strategy to initiate carboxylation. Trimethylaluminium is able to insert into unbiased aliphatic internal alkynes with syn fashion directed by ether directing group. Vinyl copper complexes are formed by transmetallation and carboxylation is realized with a similar pathway giving tetrasubstituted aliphatic vinyl carboxylic acids. In this case, regioslectivity is controlled by the favor of six-membered aluminum ring formation. Furthermore, carboxylation can be achieved on ynamides and allenamides using less reactive dimethyl zinc via similar approach.