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首页> 外文期刊>Organometallics >Alkylaluminum Complexes as Precatalysts in Hydroboration of Nitriles and Carbodiimides
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Alkylaluminum Complexes as Precatalysts in Hydroboration of Nitriles and Carbodiimides

机译：烷基铝配合物作为腈和碳二亚胺氢化物的催化剂

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摘要

The metathesis reaction of aluminum(III) dihydride LAlH2 (1) (L = (ArNCMe)(2)CH, Ar = 2,6-i-Pr2C6H4) with n-BuLi and n-Bu2Mg, respectively, resulted in di-n-butyl aluminum complex LAl(n-Bu)(2) (2). Meanwhile 1 reacted with MeLi producing dimethyl aluminum LAlMe2 (3). Complexes 2 and 3 were characterized by NMR and elemental analysis, and 2 was additionally studied by single-crystal X-ray diffraction. The reported synthesis allows for access of dialkylaluminum complexes from aluminum-(III) dihydride compound (1) with excellent yields. The chemoselective double hydroboration of nitriles or single hydroboration of carbodiimides was studied with pinacolborane (HBpin) using LAl(n-Bu)(2) (2) as the precatalyst to afford bis(boryl)amines (4a-4m) and N-borylamines (6a-6d) under solvent-free and mild conditions (60 degrees C). The records show that the catalytic reactions proceed in quantitative yields and short time. Moreover, nearly quantitative yield of di(bory1)(silyl)amine (5) was obtained, when cyanobenzene was reacted with equal amounts of HBpin and phenylsilane in the presence of precatalsyt 2. A comparison of the previously reported hydroboration reactions with nitriles in the literature and our results in the presence of the precatalyst LAl(n-Bu)(2) show convincingly the better results of short reaction time, mild reaction conditions, and quantitative yields.
机译：铝（III）二氢化氢LALH2（1）（L =（ARNNCME）（2）CH，AR = 2,6-I-PR2C6H4）分别具有n-Buli和N-Bu2Mg的复分解反应，导致Di-N. - 丁基铝复合物LAL（N-BU）（2）（2）。同时1与熔融产生二甲基铝LALME2（3）反应。复合物2和3的特征在于NMR和元素分析，通过单晶X射线衍射另外研究2。报道的合成允许从铝 - （III）二氢化铝化合物（1）具有优异产率的二烷基铝配合物。腈或碳二亚胺的单硼氢化的化学选择性双硼氢化用频哪醇使用LAL（正丁基）（2）（HBpin）（2）研究作为前段催化剂，得到双（硼烷基）胺（4A-4M）和N- borylamines （6a-6d）在无溶剂和温和条件下（60℃）。记录表明，催化反应在定量产率和短时间内进行。此外，获得几乎定量的DI（Bory1）（甲硅烷基）胺（5）的产率，当在precatalsyt的情况下用相等量的HBPIN和苯基硅烷反应时，将先前报道的水合反应与腈的相比进行了比较文献和我们在预催化剂LAL（N-BU）（2）的存在下的结果表明了令人信服的短反应时间，温和反应条件和定量产率的更好结果。

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  • 来源
    《Organometallics》 |2019年第15期|共6页
  • 作者

    Ding Yi; Ma Xiaoli; Liu Yashuai; Liu Wenqing; Yang Zhi; Roesky Herbert W.;

  • 作者单位

    Beijing Inst Technol Sch Chem &

    Chem Engn Beijing 100081 Peoples R China;

    Beijing Inst Technol Sch Chem &

    Chem Engn Beijing 100081 Peoples R China;

    Beijing Inst Technol Sch Chem &

    Chem Engn Beijing 100081 Peoples R China;

    Beijing Inst Technol Sch Chem &

    Chem Engn Beijing 100081 Peoples R China;

    Beijing Inst Technol Sch Chem &

    Chem Engn Beijing 100081 Peoples R China;

    Georg August Univ Inst Anorgan Chem D-37077 Gottingen Germany;

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