Goettel James T, Gao Haopeng, Dotzauer Simon, Braunschweig Holger
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2020 Jan 22;26(5):1136-1143. doi: 10.1002/chem.201904715. Epub 2020 Jan 9.
A cyclic (alkyl)(amino)carbene (CAAC) has been shown to react with a covalent azide similar to the Staudinger reaction. The reaction of CAAC with trimethylsilyl azide afforded the N-silylated 2-iminopyrrolidine ( CAAC=NSiMe ), which was fully characterized. This compound undergoes hydrolysis to afford the 2-iminopyrrolidine and trimethylsiloxane which co-crystallize as a hydrogen-bonded adduct. The N-silylated 2-iminopyrrolidine was used to transfer the novel pyrrolidine-2-iminato ligand onto both main-group and transition-metal centers. The reaction of the tetrabromodiborane bis(dimethyl sulfide) adduct with two equivalents of CAAC=NSiMe afforded the disubstituted diborane. The reaction of CAAC=NSiMe with TiCl and CpTiCl afforded CAAC=NTiCl and CAAC=NTiCl Cp, respectively.
一种环状（烷基）（氨基）卡宾（CAAC）已被证明可与类似于施陶丁格反应的共价叠氮化物发生反应。CAAC与三甲基硅基叠氮化物反应生成了N-硅烷基化的2-亚氨基吡咯烷（CAAC=NSiMe），并对其进行了全面表征。该化合物发生水解生成2-亚氨基吡咯烷和三甲基硅氧烷，它们以氢键加合物的形式共结晶。N-硅烷基化的2-亚氨基吡咯烷用于将新型吡咯烷-2-亚氨基配体转移到主族和过渡金属中心上。四溴二硼烷双（二甲基硫醚）加合物与两当量的CAAC=NSiMe反应生成二取代二硼烷。CAAC=NSiMe与TiCl和CpTiCl反应分别生成CAAC=NTiCl和CAAC=NTiCl Cp。
