A nickel-catalyzed direct cage B-H poly-chalcogenation of icosahedral carborane clusters,enabled by a variable bidentate 8-aminoquinoline traceless directing group(TDG),has been developed under oxidantfree and weakly ...A nickel-catalyzed direct cage B-H poly-chalcogenation of icosahedral carborane clusters,enabled by a variable bidentate 8-aminoquinoline traceless directing group(TDG),has been developed under oxidantfree and weakly basic conditions,resulting in poly-thiolated/selenylated o-carboranes present in boron delivery agents for boron neutron capture therapy(BNCT).The controllable selectivity of removal and retention of these TDGs was achieved through simple substrate structure modification(C2-substitution in o-carboranes).A wide range of disulfides,diselenides,thiophenols and benzeneselenols,as well as o-carborane substrates,are compatible,generating diversely functionalized o-carboranes with tetra-and trichalcogen substitution.The current protocol opens new avenues for oxidant-and strong base-free,base-metal-catalyzed regioselective iterative B-H chalcogenation of carboranes via a variable bidentate TDG strategy.展开更多
基金Hainan University(KYQD(ZR)1958)the https://dx.doi.org/10.13039/501100001809(22161015)the Hainan Provincial Natural Science Foundation of China(221RC448)for financial support.
文摘A nickel-catalyzed direct cage B-H poly-chalcogenation of icosahedral carborane clusters,enabled by a variable bidentate 8-aminoquinoline traceless directing group(TDG),has been developed under oxidantfree and weakly basic conditions,resulting in poly-thiolated/selenylated o-carboranes present in boron delivery agents for boron neutron capture therapy(BNCT).The controllable selectivity of removal and retention of these TDGs was achieved through simple substrate structure modification(C2-substitution in o-carboranes).A wide range of disulfides,diselenides,thiophenols and benzeneselenols,as well as o-carborane substrates,are compatible,generating diversely functionalized o-carboranes with tetra-and trichalcogen substitution.The current protocol opens new avenues for oxidant-and strong base-free,base-metal-catalyzed regioselective iterative B-H chalcogenation of carboranes via a variable bidentate TDG strategy.
