文献类型：期刊文献

英文题名：A Pd-Catalyzed Route to Neutral and Anionic Aminated Carboranes

作者：Wang, Ya-Nan[1];Chen, Ren[1];Wang, Ruo-Xuan[1];Dong, Beibei[1];Huang, Xule[1];Zou, Chao[2];Mu, Xin[1,3]

机构：[1]East China Univ Sci & Technol, Sch Pharm, Shanghai 200237, Peoples R China;[2]Songshan Lake Mat Lab, Frontier Res Ctr, Funct Coordinat Mat Grp, Dongguan 523808, Guangdong, Peoples R China;[3]Engn Res Ctr Pharmaceut Proc Chem, Minist Educ, Shanghai 200237, Peoples R China

年份：2026

卷号：45

期号：11

起止页码：1295

外文期刊名：ORGANOMETALLICS

收录：;EI(收录号：20262320864718);WOS:【SCI-EXPANDED(收录号:WOS:001768511100001)】；

基金：The authors are grateful for financial support from the Natural Science Foundation of Shanghai (22ZR1416700), the open research fund of Songshan Lake Materials Laboratory (2023SLABFN12), and the Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education. We are grateful for instrumental support from the Research Center of Analysis and Test, East China University of Science and Technology.

语种：英文

外文关键词：Amination - Boron - Catalysis - Catalysts - Chemical bonds - Cyclization - Ligands - Medicinal chemistry - Palladium compounds - Phosphorus compounds - Scaffolds - Scaffolds (biology) - Sulfur compounds

摘要：Functionalization of boron-rich clusters, such as icosahedral ortho-carborane, with nitrogen-containing groups is essential for advancing their use in medicinal research and materials science. A key challenge for the amination is that ortho-carborane readily undergoes deboronation under basic conditions, forming anionic nido-carborane species that deactivate metal catalysts. In this study, we developed a general protocol to achieve mono- and vicinal diamination of ortho-carborane under Pd-catalyzed cross-coupling conditions. Electron-rich triaryl phosphine ligands were found to significantly improve the reaction efficiency and minimize the uncontrolled deboronation. The resulting vicinally diaminated ortho-carboranes can undergo oxidative cyclization to form carborane-fused six-membered heterocycles. Furthermore, controlled deboronation of both the diamination products and the carborane-fused heterocycles afforded a range of anionic nido-carborane derivatives. Under anodic oxidation conditions, oxidative bond formation in the presence of pyridine derivatives, disulfide, and PPh3 was achieved efficiently, generating previously inaccessible trisubstituted nido-carboranes. The incorporation of a biological ligand in a diaminated nido-carborane demonstrates the potential applications of these new boron cluster scaffolds in medicinal chemistry.