Abstract The previously reported active Lewis pair (ALP) i Bu2Al–N(2-Ad)NC5H10 (1) (2-Ad = 2-adamantyl) is readily accessible by hydroalumination of the hydrazone H10C5N–N=(2-C10H14) with H–Al i Bu2. Treatment of 1 with two equivalents of isocyanates R-N=C=O yields six-membered AlC2N2O heterocycles 2 (2a, R = Ph; 2b, R = p-Tol) by dual insertion into the Al–N bonds. 2a reacts as a nucleophile with carboxylic acid chlorides R-C(O)–Cl [R = CH2 t Bu, p-Tol, H2CCH(Me)C6H4(4-CH2CHMe2) (Ibu-profen acid chloride), 0.5 (1,4-C6H4)] to afford by elimination of i Bu2AlCl and hydrolysis new triuret derivatives R-C(O)[N(Ph)C(O)]2–N(2-Ad)NC5H10 (3a to 3d) as colourless, sparingly soluble solids in moderate (3c) to high (3b) yields. The analogous reaction of 2a with (p-Tol)–C(Cl)=N(p-Tol) leads to the imidoyl derivative (p-Tol)N=C(p-Tol)[N(Ph)C(O)]2–N(2-Ad)NC5H10 (4a), which showed a fast exchange of phenyl and tolyl groups to yield a mixture of isomers. The analogous reaction of 2b affords the corresponding compound 4b for which a single isomer is isolated despite the scrambling of substituents.

中文翻译：

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基于 Al/N 的活性路易斯对：异氰酸酯插入产物作为高效亲核试剂用于轻松生成高功能分子

摘要 先前报道的活性路易斯对 (ALP) i Bu2Al–N(2-Ad)NC5H10 (1) (2-Ad = 2-adamantyl) 很容易通过腙 H10C5N–N=(2-C10H14) 的氢铝化而获得H-Al i Bu2。用两当量的异氰酸酯 RN=C=O 处理 1，通过双插入 Al-N 键产生六元 AlC2N2O 杂环 2（2a，R = Ph；2b，R = p-Tol）。2a 作为亲核试剂与羧酸氯化物 RC(O)–Cl [R = CH2 t Bu, p-Tol, H2CCH(Me)C6H4(4-CH2CHMe2) (Ibu-profen 酰氯), 0.5 (1,4- C6H4)] 通过消除 i Bu2AlCl 和水解得到新的三脲衍生物 RC(O)[N(Ph)C(O)]2–N(2-Ad)NC5H10（3a 至 3d），在中等 (3c) 到高 (3b) 产量。2a 与 (p-Tol)–C(Cl)=N(p-Tol) 的类似反应生成亚胺基衍生物 (p-Tol)N=C(p-Tol)[N(Ph)C(O) ]2–N(2-Ad)NC5H10 (4a)，显示出苯基和甲苯基的快速交换以产生异构体的混合物。2b 的类似反应提供了相应的化合物 4b，尽管有取代基的混杂，但分离出单个异构体。