碳硼烷是由碳氢和硼氢顶点组成的笼状分子, 在医药、能源和材料等领域有着重要应用, 但目前在碳硼烷硼顶点引入杂原子取代基的方法还较为有限. 基于此, 本工作从3-碘-邻-碳硼烷出发, 通过钯催化烯基化、金属迁移及后续与杂原子亲核试剂的偶联反应, 一锅法构筑硼碳键和硼杂原子键, 成功实现了一系列新型3-烯基-4-胺基/烷氧基/烷(芳)硫基-邻-碳硼烷衍生物的合成.

Icosahedral carboranes are carbon-boron molecular clusters, sharing many features with benzene such as aromaticity, high thermal and chemical stability. On the other hand, carboranes have their own unique characteristics like spherical geometry and three-dimensional electronic delocalization. These properties render carboranes unique building blocks for various applications ranging from versatile ligands to functional materials to medicine. In this regard, functionalization of carboranes, particularly regioselective functionalization of cage B-vertexes has recently received much attention. Based on our recently developed Pd-catalyzed iodine-migration on o-carborane cage, a Pd-catalyzed regioselective difunctionalization of 3-iodo-o-carborane in a one-pot manner has been achieved to afford a series of 3-alkenyl-4-Nu-o-carboranes (Nu=arylamino, alkoxyl, alkyl and arylthio) in 47%~99% yields. This protocol combines the sequential activation of cage B(3)—I and B(4)—H bonds by Pd migration, as well as further Pd-catalyzed transformation of B(4)—I bond, leading to the construction of B—C and B—Heteroatom bonds. A general procedure for the synthesis of 3-alkenyl-4-Nu-o-carboranes is described as follows: to a tetrahydrofuran (THF) solution (1 mL) of NuH (1.0 mmol) was added base (1.0 mmol) at 0 ℃ under an atmosphere of dry nitrogen. The reaction mixture was stirred for another 10 min to obtain the NuM solution (NuM=ArNHMgBr, base=EtMgBr; NuM=Ar₂NLi, base=ⁿBuLi). Another oven-dried Schlenk flask equipped with a stir bar was charged with 3-iodo-o-carborane (1, 27 mg, 0.1 mmol), Pd(PPh₃)₄ (12 mg, 0.01 mmol), diphenylacetylene (89 mg, 0.5 mmol) and dry toluene (1 mL) under an atmosphere of dry nitrogen. The flask was closed, and stirred at 80 ℃ for 72 h. Then, the resulting solution was cooled to 0 ℃, to which was slowly added NuM (0.15 mmol) (NuM=ArNHMgBr, Ar₂NLi, ^tBuONa and RSNa). The reaction mixture was warmed to room temperature, and stirred at 80 ℃ for 24 h. After quenching with water (1 mL) and extraction with ethyl acetate (5 mL×3), the organic portions were combined and concentrated to dryness in vacuo. The residue was subjected to flash column chromatography on silica gel (300~400 mesh) using n-hexane as eluent to give the product.