Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Fac. de Ciencias, Edificio D, Pedro Cerbuna 12, 50009 Zaragoza (Spain), Fax: (+34) 976761187.
Departament de Química, Edifici Cn, Universitat Autònoma de Barcelona, 08193 Cerdanyola del Vallés, Barcelona (Spain), Fax: (+34) 935812920.
Chemistry. 2015 Jun 1;21(23):8626-36. doi: 10.1002/chem.201500338. Epub 2015 Apr 27.
The oxidative coupling of primary amines with internal alkynes catalyzed by Ru complexes is presented as a general atom-economy methodology with a broad scope of applications in the synthesis of N-heterocycles. Reactions proceed through regioselective C-H bond activation in 15 minutes under microwave irradiation or in 24 hours with conventional heating. The synthesis of 2,3,5-substituted pyridines, benzo[h]isoquinolines, benzo[g]isoquinolines, 8,9-dihydro-benzo[de]quinoline, 5,6,7,8-tetrahydroisoquinolines, pyrido[3,4g]isoquinolines, and pyrido[4,3g]isoquinolines is achievable depending on the starting primary amine used. DFT calculations on a benzylamine substrate support a reaction mechanism that consists of acetate-assisted C-H bond activation, migratory-insertion, and C-N bond formation steps that involve 28-30 kcal mol(-1) . The computational study is extended to additional substrates, namely, 1-naphthylmethyl-, 2-methylallyl-, and 2-thiophenemethylamines.
钌配合物催化的伯胺与内炔的氧化偶联被提出作为一种通用的原子经济性方法，在 N-杂环化合物的合成中有广泛的应用。反应在微波辐射下 15 分钟或在常规加热下 24 小时内通过区域选择性 C-H 键活化进行。根据所用的起始伯胺，可以合成 2,3,5-取代吡啶、苯并[h]异喹啉、苯并[g]异喹啉、8,9-二氢-苯并[de]喹啉、5,6,7,8-四氢异喹啉、吡啶并[3,4g]异喹啉和吡啶并[4,3g]异喹啉。对苄基胺底物的 DFT 计算支持一种反应机理，该机理包括乙酸盐辅助的 C-H 键活化、迁移插入和 C-N 键形成步骤，涉及 28-30 kcal mol(-1)。该计算研究扩展到其他底物，即 1-萘甲基胺、2-甲基烯丙基胺和 2-噻吩甲基胺。
