Sarkar Nabin, Bera Subhadeep, Nembenna Sharanappa
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Homi Bhabha National Institute (HBNI), Bhubaneswar 752 050 India.
J Org Chem. 2020 Apr 3;85(7):4999-5009. doi: 10.1021/acs.joc.0c00234. Epub 2020 Mar 23.
The reaction of LH [L = {(ArNH)(ArN)-C=N-C=(NAr)(NHAr)}; Ar =2,6-Et-CH] with a commercially available alane amine adduct (HAl·NMeEt) in toluene resulted in the formation of a conjugated bis-guanidinate (CBG)-supported aluminum dihydride complex, i.e., LAlH (), in good yield. The new complex has been thoroughly characterized by multinuclear magnetic resonance, IR, mass, and elemental analyses, including single-crystal structural studies. Further, we have demonstrated the aluminum-catalyzed hydroboration of a variety of nitriles and alkynes. Moreover, aluminum-catalyzed hydroboration is expanded to more challenging substrates such as alkene, pyridine, imine, carbodiimide, and isocyanides. More importantly, we have shown that the aluminum dihydride catalyzed both intra- and intermolecular chemoselective hydroboration of nitriles and alkynes over other reducible functionalities for the first time.
LH[L = {(ArNH)(ArN)-C=N-C=(NAr)(NHAr)}；Ar = 2,6 - Et - CH]与市售的铝烷胺加合物（HAl·NMeEt）在甲苯中反应，以良好的产率生成了一种共轭双胍基（CBG）支撑的二氢化铝配合物，即LAlH（）。该新型配合物已通过多核磁共振、红外光谱、质谱和元素分析进行了全面表征，包括单晶结构研究。此外，我们还展示了铝催化的多种腈和炔烃的硼氢化反应。而且，铝催化的硼氢化反应扩展到了更具挑战性的底物，如烯烃、吡啶、亚胺、碳二亚胺和异氰化物。更重要的是，我们首次表明二氢化铝能催化腈和炔烃分子内和分子间的化学选择性硼氢化反应，优于其他可还原官能团。
