Würtemberger-Pietsch Sabrina, Schneider Heidi, Marder Todd B, Radius Udo
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2016 Sep 5;22(37):13032-6. doi: 10.1002/chem.201603328. Epub 2016 Aug 9.
We report the reactions of catecholborane (HBcat; 1) with unsaturated and saturated NHCs as well as CAAC(Me) . Mono-NHC adducts of the type HBcat⋅NHC (NHC=nPr2 Im, iPr2 Im, iPr2 Im(Me) , and Dipp2 Im) were obtained by stoichiometric reactions of HBcat with the unsaturated NHCs. The reaction of CAAC(Me) with HBcat yielded the B-H activated product CAAC(Me) (H)Bcat via insertion of the carbine-carbon atom into the B-H bond. The saturated NHC Dipp2 SIm reacted in a 2:2 ratio yielding an NHC ring-expanded product at room temperature forming a six-membered -B-C=N-C=C-N- ring via C-N bond cleavage and further migration of the hydrides from two HBcat molecules to the former carbene-carbon atom.
我们报道了儿茶酚硼烷（HBcat；1）与不饱和及饱和氮杂环卡宾（NHC）以及环状（烷基）（氨基）卡宾（CAAC(Me)）的反应。通过HBcat与不饱和NHC的化学计量反应，得到了HBcat⋅NHC类型的单-NHC加合物（NHC = nPr2Im、iPr2Im、iPr2Im(Me)和Dipp2Im）。CAAC(Me)与HBcat反应，通过卡宾碳原子插入B-H键生成了B-H活化产物CAAC(Me)(H)Bcat。饱和NHC Dipp2SIm以2:2的比例反应，在室温下生成一种NHC扩环产物，通过C-N键断裂形成一个六元-B-C=N-C=C-N-环，并且两个HBcat分子的氢化物进一步迁移至先前的卡宾碳原子上。
