Insertion of polar and nonpolar unsaturated molecules into carbon-rhenium bonds generated by C-H bond activation: Synthesis of phthalimidine and indene derivatives
Insertion of polar and nonpolar unsaturated molecules into carbon-rhenium bonds generated by C-H bond activation: Synthesis of phthalimidine and indene derivatives
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DOI：
10.1021/ja054216i
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发表时间：
2006-01-11
影响因子：
15
通讯作者：
Takai, K
中科院分区：
文献类型：
--
作者：
Kuninobu, Y;Tokunaga, Y;Takai, K
[ReBr（CO）（3）（thf）]（2）催化芳香醛亚胺与异氰酸酯和乙炔的反应，分别以定量产率得到苯并[c]吡咯酮和茚衍生物。该反应通过C-H键活化、异氰酸酯或乙炔的插入、分子内亲核环化为所产生的酰胺基或烯基-氨基物种的醛亚胺以及还原消除来进行。与通常用于这种类型的反应的钌和铑催化剂相反，该催化剂促进极性不饱和分子的插入。这比插入非极性不饱和分子更容易发生。
A rhenium complex, [ReBr(CO)(3)(thf)](2), catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, intramolecular nucleophilic cyclization to the aldimine of the generated amido- or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the insertion of a polar unsaturated molecule. This occurs more easily than the insertion of a nonpolar unsaturated molecule.