Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light.
Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light.
复制标题
DOI：
10.1002/anie.202210772
复制
发表时间：
2022-12-12
影响因子：
16.6
通讯作者：
Alexanian, Erik J.
中科院分区：
文献类型：
--
作者：
Veatch, Alexander M.;Liu, Shubin;Alexanian, Erik J.
通过C（sp2）-N裂解的芳基亲电试剂的催化羰基化仍然是一个重大挑战。在此，我们展示了一个简单的钴催化剂的可见光促进苯胺衍生的三烷基铵盐的氨羰基化。该反应在适合于后期官能化的温和条件下进行，并且能够直接从苯胺进行套叠羰基化。一系列的烷基胺是成功的合作伙伴，烷氧基羰基化也被证明。机理研究和密度泛函理论计算支持了一种新的芳基亲电试剂催化羰基化反应机理，该机理涉及一个关键的可见光诱导羰基光解离。我们证明了钴催化的氨基羰基化苯胺衍生的三烷基铵盐促进可见光通过具有挑战性的C（sp2）-N裂解。该反应适合于后期官能化，并且适合于直接从苯胺进行的套叠羰基化。机理研究和密度泛函理论计算支持一种新的机制，涉及一个关键的可见光诱导的羰基光解和SNAr型氧化加成。
Catalytic carbonylations of aryl electrophiles via C(sp2)–N cleavage remains a significant challenge. Herein, we demonstrate an aminocarbonylation of aniline-derived trialkylammonium salts promoted by visible light with a simple cobalt catalyst. The reaction proceeds under mild conditions suitable for late-stage functionalization and is amenable to telescoped carbonylations directly from anilines. A range of alkylamines are successful partners, and alkoxycarbonylation is also demonstrated. Mechanistic studies and DFT calculations support a novel mechanism for catalytic carbonylations of aryl electrophiles involving a key visible light-induced carbonyl photodissociation. We demonstrate a cobalt-catalyzed aminocarbonylation of aniline-derived trialkylammonium salts promoted by visible light via a challenging C(sp2)–N cleavage. The reaction is suitable for late-stage functionalization and is amenable to telescoped carbonylations directly from anilines. Mechanistic studies and DFT calculations support a novel mechanism involving a key visible light-induced carbonyl photodissociation and SNAr-type oxidative addition.
登录
查看更多内容
影响因子：
3.6
作者：
BRUNET, JJ;SIDOT, C;CAUBERE, P
通讯作者：
CAUBERE, P
Sonogashira 芳基三甲基铵盐的交叉偶联
影响因子：
12.9
作者：
Chen, Qianwei;Gao, Fengchen;Cao, Changsheng
通讯作者：
Cao, Changsheng
影响因子：
5.4
作者：
Gosset, Cyrille;Pellegrini, Sylvain;Pelinski, Lydie
通讯作者：
Pelinski, Lydie
影响因子：
3.6
作者：
BRUNET, JJ;SIDOT, C;CAUBERE, P
通讯作者：
CAUBERE, P
影响因子：
5.2
作者：
Kong, Xianqiang;Chen, Yiyi;Cao, Zhong-Yan
通讯作者：
Cao, Zhong-Yan