Lewis Acid/Metal Amide Hybrid as an Efficient Catalyst for Carbon-Carbon Bond Formation
Lewis Acid/Metal Amide Hybrid as an Efficient Catalyst for Carbon-Carbon Bond Formation
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路易斯酸/金属酰胺杂化物作为碳-碳键形成的有效催化剂
DOI：
10.1039/c4sc01332h
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发表时间：
2014
期刊：
影响因子：
8.4
通讯作者：
Shu Kobayashi
中科院分区：
文献类型：
--
作者：
Yasuhiro Yamashita;Yuki Saito;Takaki Imaizumi;Shu Kobayashi
虽然刘易斯酸和金属酰胺是最常用的金属物质，但据信它们在组合时不相容。在这里，我们描述了一种刘易斯酸/金属酰胺杂化物，它包含吸电子基团和碱性和庞大的氮官能团在同一个金属配合物，作为一种新型的催化剂。本文合成了In（N（SiMe 3）2）2 Cl（In（HMDS）2 Cl）和In（HMDS）2 OTf两种刘易斯酸/金属氨基化合物，它们对硝酮与端炔反应合成炔丙基羟胺具有良好的催化活性。值得注意的是，无论是刘易斯酸（InCl 3，In（OTf）3）还是金属酰胺（In（HMDS）3）都没有活性;只有杂化物工作良好，并且杂化物的催化活性显示出比先前报道的用于该反应的催化剂的催化活性高得多。作为催化剂的刘易斯酸/金属酰胺杂化物的概念可以扩展到宽的酸/碱催化。
While Lewis acids and metal amides are among the most frequently used metal species, they are believed to be incompatible when combined. Here we describe a Lewis acid/metal amide hybrid, which contains electron-withdrawing groups and basic and bulky nitrogen functional groups in the same metal complex, as a novel catalyst. We have synthesized In(N(SiMe3)2)2Cl (In(HMDS)2Cl) and In(HMDS)2OTf as Lewis acid/metal amide hybrids, which showed excellent catalytic activity for the reaction of nitrones with terminal alkynes to give synthetically useful propargyl hydroxylamines. It is noted that neither the Lewis acids (InCl3, In(OTf)3) nor the metal amides (In(HMDS)3) have activity; only the hybrids worked well, and the catalytic activity of the hybrids was shown to be much higher than that of previously reported catalysts for this reaction. The concept of a Lewis acid/metal amide hybrid as a catalyst may be expanded to broad acid/base catalysis.