Synthesis of Amido-N-imidazolium Salts and their Applications as Ligands in Suzuki-Miyaura Reactions: Coupling of Hetero-aromatic Halides and the Synthesis of Milrinone and Irbesartan
Synthesis of Amido-N-imidazolium Salts and their Applications as Ligands in Suzuki-Miyaura Reactions: Coupling of Hetero-aromatic Halides and the Synthesis of Milrinone and Irbesartan
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DOI：
10.1002/adsc.201000592
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发表时间：
2010-12-17
影响因子：
5.4
通讯作者：
Lee, Sunwoo
中科院分区：
文献类型：
--
作者：
Kumar, Manian Rajesh;Park, Kyungho;Lee, Sunwoo
介绍了一种新的以钯-酰胺- n -杂环碳烷为催化剂的杂芳基溴化合物Suzuki-Miyaura偶联反应催化体系。以相应的苯胺为原料，高收率地合成了多种立体体积大的氨基- n -咪唑盐。该催化体系有效地促进了杂芳基溴化物和氯化物与一系列硼酸的Suzuki-Miyaura偶联反应，得到相应的芳基化合物，产率高。产率随取代基空间体积的增加而增加。特别是1-（2,6-二异丙基苯基）-3- n -（2,4,6-三叔丁基苯乙酰胺）咪唑溴（4bc）在2-溴吡啶与苯硼酸的偶联反应中表现出85万TON。此外，以立体体积大的氨基- n -咪唑盐（4bc）为配体，通过Suzuki-Miyaura偶联法合成了米立酮和厄贝沙坦等药物化合物。
A new catalytic system based on palladium-amido-N-heterocyclic carbenes for Suzuki-Miyaura coupling reactions of heteroaryl bromides is described. A variety of sterically bulky, amido-N-imidazolium salts were synthesized in high yields from the corresponding anilines. This catalytic system effectively promoted Suzuki-Miyaura couplings of heteroaryl bromides and chlorides with a range of boronic acids to give the corresponding aryl compounds in high yield. The yield was increased with increasing steric bulkiness of the substituted group. Especially, 1-(2,6-diisopropylphenyl)-3-N-(2,4,6-tri-tert-butylphenylacetamido)imidazolium bromide (4bc) exhibited 850,000 TON in the coupling reaction of 2-bromopyridine and phenylboronic acid. In addition, pharmaceutical compounds such as milrinone and irbesartan were synthesized via Suzuki-Miyaura coupling using sterically bulky, amido-N-imidazolium salt (4bc) as a ligand.