Sonogashira Cross-Coupling of Aryltrimethylammonium Salts
Sonogashira Cross-Coupling of Aryltrimethylammonium Salts
复制标题
Sonogashira 芳基三甲基铵盐的交叉偶联
DOI：
10.1021/acscatal.9b00218
复制
发表时间：
2019-04-01
期刊：
影响因子：
12.9
通讯作者：
Cao, Changsheng
中科院分区：
文献类型：
--
作者：
Chen, Qianwei;Gao, Fengchen;Cao, Changsheng
本文报道了以三氟甲磺酸芳基三甲铵为亲电偶联剂，通过Sonogashira偶联反应裂解C-N键形成C（sp）-C（sp（2））键的方法。反应在温和的条件下进行良好的化学计量比的烷基，芳基，或杂芳基乙炔，并提供高达93%的产率。在反应条件下容许许多有用的官能团。直接胺炔基化可以通过一锅法实现，而无需分离铵盐。该方案可以在克规模上进行。通过密度泛函理论计算研究了反应机理，包括氧化加成、炔配位、去质子化和还原消除，得到了交叉偶联产物.
A protocol for C(sp)-C(sp(2)) bond formation via the Sonogashira coupling reaction involving C-N bond cleavage with aryltrimethylammonium triflate as an electrophilic coupling partner is described in this work. The reactions proceeded well under mild conditions with a stoichiometric ratio of alkyl, aryl, or heteroaryl acetylenes and provided yields of up to 93%. Numerous useful functional groups were tolerated under the reaction conditions. Direct amine alkynylation can be achieved through a onepot process without the isolation of ammonium salt. The protocol can be performed on a gram scale. Density functional theory calculations were performed to investigate the reaction mechanism that involved oxidative addition, alkyne coordination, deprotonation, and reductive elimination, which yielded the cross-coupling product.