Chen Shimin, Li Bin, Wang Xiaoping, Huang Yanting, Li Jiancheng, Zhu Hongping, Zhao Lili, Frenking Gernot, Roesky Herbert W
State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 211816, P. R. China.
Chemistry. 2017 Oct 4;23(55):13633-13637. doi: 10.1002/chem.201703804. Epub 2017 Sep 7.
The 2-aminophenylaluminum dihydride (2-TMP-C H )AlH (2) has been prepared and characterized for the first time. Compound 2 features an intramolecular N⋅⋅⋅Al donor-acceptor bond. 2 reacted with N-methylpyrrole and N-methylindole (both at 50 °C) by means of the elusive AlH C(sp )-H dehydroalumination to aluminum heteroaryls (3 and 4). Moreover, 2 reacted with PhCCSiMe (at room temperature) and Ph CCNR (R=iPr or 2,6-iPr C H , at -30 to 20 °C ) to yield aluminaindene heterocycle (8) and alumina-aza-naphthalene heterocycle (9 and 10), respectively. These reactions underwent hydroalumination followed by AlH C(sp )-H dehydroalumination. The reaction mechanism has been studied by combining experiment and quantum chemical calculations, with the result that the key heteroarene or arene C(sp )-H bond activation is involved under cooperative interaction by the inherent N/Al donor/acceptor pair. The reported reactions open a straightforward route to heteroaryl and unique heterocyclic aluminum compounds.
二氢-2-氨基苯基铝（2-TMP-C₆H₄）AlH₂（2）首次被制备并表征。化合物2具有分子内N∙∙∙Al供体-受体键。2与N-甲基吡咯和N-甲基吲哚（均在50 °C）通过难以捉摸的AlH C(sp³)-H脱氢铝化反应生成铝杂芳基化合物（3和4）。此外，2与PhCCSiMe₃（在室温下）以及Ph₂CCNR（R = iPr或2,6-iPr₂C₆H₃，在-30至20 °C）反应，分别生成铝茚杂环化合物（8）和铝氮杂萘杂环化合物（9和10）。这些反应经历了氢化铝化，随后是AlH C(sp³)-H脱氢铝化。通过结合实验和量子化学计算对反应机理进行了研究，结果表明关键的杂芳烃或芳烃C(sp³)-H键活化是在固有的N/Al供体/受体对的协同作用下发生的。所报道的反应为合成杂芳基和独特的杂环铝化合物开辟了一条直接的途径。
