Grant: Discovery Grants Program - Individual

Bismuth (Bi), the 83rd element of the periodic table, is the heaviest stable, non-toxic and non-radioactive element of the periodic table. This heavy element possesses a dual behavior that sits between a metal and a classic pnictogen. Organobismuth compounds (species that contain one or multiple C-Bi bonds) were abundantly utilized by Barton, Finet and Dodonov in the 1980s to transfer phenyl groups (-C6H6) to organic compounds. Recently, these species have undergone a spectacular renaissance with the work of Burford in Canada, Dostál in Czech Republic, Ball in the UK and Lichtenberg and Cornella in Germany. The intense research going on worldwide in organobismuth chemistry is an indication of the renewed interest for this class of underexplored compounds and the diversified and unique chemistry that is accessible with them. Over the past years, we established a strong research program on the development of reactions involving organobismuth compounds that result in the formation of C(sp2)-C(sp2), C(sp2)-C(sp3), N-C(sp2), N-C(sp3), O-C(sp2) and S-C(sp3) bonds. Our activities related to bismuth chemistry established ourselves as leaders in the field. In this research program, we propose to depart from chemistry designed from a priori predictions based on literature precedents and enter unexplored territories. Our objectives are to prepare unprecedented bismuth compounds that will mimic transition metals and to use them to perform reactions for which there are currently no solution. First, we will prepare neutral and cationic trivalent and pentavalent cyclopropylbismuth derivatives and use them in cyclopropylation reactions using scaffolds that are of interest to medicinal chemists. Secondly, we will construct an unsymetrical pincer amido-imino bismuth compound that will allow the transfer of aryl and cyclopropyl groups in an atom economical way via a recycling process. Third, we will prepare cyclopropyl-, alkynyl-, alkenyl- and trifluoromethyl bismacycles and use them to transfer small groups to phenols, thiophenols, indoles and pyridones. Fourth, we will synthesize a bismacyclic compound that possesses a chiral alkyl group attached to the bismuth R*-Bi and investigate its fate in palladium-catalyzed cross-coupling reactions. Last, we will utilize a low-valent Bi(I) complex to perform the hydrosilylation, hydroboration and cyclopropanation of alkenes. A chiral version will be developed using a chiral pincer ligand. Some of these projects will be done in collaboration with experts in the field in the UK, Czech Republic and Germany. This research program will greatly contribute to the advancement of knowledge in the field of bismuth chemistry and will provide solutions to reactions that cannot currently be accomplished. The reactions that will be developed here will find application in medicinal chemistry where they will facilitate the preparation of bioactive compounds. This program will contribute to the training of highly qualified scientists.