碘化亚铜/4-羟基-L-脯氨酸作为一种更有效的催化体系，用于芳基溴化物与N-叔丁氧羰基肼及氨水的偶联反应。

CuI/4-hydro-L-proline as a more effective catalytic system for coupling of aryl bromides with N-boc hydrazine and aqueous ammonia.

作者信息

Jiang Liqin, Lu Xu, Zhang Hui, Jiang Yongwen, Ma Dawei

机构信息

State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China.

出版信息

J Org Chem. 2009 Jun 19;74(12):4542-6. doi: 10.1021/jo9006738.

DOI:10.1021/jo9006738

PMID:19432437

Abstract

CuI/4-hydroxy-l-proline-catalyzed coupling of aryl bromides and N-Boc hydrazine takes place in DMSO at 80 degrees C to give N-aryl hydrazides. When aryl iodides are employed, this reaction completes at 50 degrees C and no ligand is required. Under the catalysis of CuI/4-hydroxy-l-proline, the coupling reaction of aqueous ammonia with aryl bromides proceeds smoothly at 50 degrees C to afford primary arylamines. In this case K(2)CO(3) is found as a better base than Cs(2)CO(3). These processes allow assembly of N-aryl hydrazides and primary arylamines that bear a wide range of functional groups including hydroxyl, amine, trifluoromethyl, ester, nitro, and ketone.

摘要

碘化亚铜/4-羟基-L-脯氨酸催化的芳基溴化物与N-叔丁氧羰基肼的偶联反应在二甲基亚砜中于80℃下进行，生成N-芳基酰肼。当使用芳基碘化物时，该反应在50℃下完成且无需配体。在碘化亚铜/4-羟基-L-脯氨酸的催化下，氨水与芳基溴化物的偶联反应在50℃下顺利进行，得到伯芳基胺。在这种情况下，发现碳酸钾比碳酸铯是更好的碱。这些过程使得能够组装带有包括羟基、胺基、三氟甲基、酯基、硝基和酮基等多种官能团的N-芳基酰肼和伯芳基胺。