The synthesis of organoboron compounds is of contemporary importance in the chemistry community given their utility in subsequent functionalization reactions as well as the growing realization of their therapeutic potential in the treatment of human disease. Redox neutral copper-catalyzed difunctionalization enables tandem addition of boron and an electrophile to unsaturated organic compounds. Recently, a catalytic reaction was devised in which CO2 and B(pin) (pin = pinacolate: 2,3-dimethyl-2,3-butanediolate) were added regioselectively across the alkene utilizing ICyCuCl as the precatalyst (ICy=(1,3-dicyclohexyl)imidazol-2-ylidene). The reaction mechanism was explored through isolation and characterization of a series of Cu(I)–alkyl complexes using the sterically and electronically similar IPr N-heterocyclic carbene ligand, (IPr=1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidene). A series of β-boryl alkyl Cu(I) complexes were prepared that demonstrate facile CO2 insertion, thus generating the catalytically prepared product. Evaluation of carboxylation rates using electronically different vinyl arene starting materials was also conducted, providing information on this step of the catalytic reaction.

Mechanistic analysis of cu(i)-catalyzed boracarboxylation of vinyl arenes

2019 Spring National Meeting

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