Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Esters
Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Esters
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DOI：
10.1021/jacs.6b12329
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发表时间：
2017-01-25
影响因子：
15
通讯作者：
Newman, Stephen G.
中科院分区：
文献类型：
--
作者：
Ben Halima, Taoufik;Zhang, Wanying;Newman, Stephen G.
Suzuki-Miyaura偶联反应由于其可靠性、化学选择性和多样性而成为最重要的C-C键形成反应之一。芳基卤化物和拟卤化物如碘化物、溴化物和三氟甲磺酸酯传统上用作亲电偶联配偶体。将反应范围扩大到非传统亲电试剂是一个持续的挑战，以使更多的有用产品能够从简单的起始材料制成。在本文中，我们提出了如何NHC-基Pd催化剂可以使铃木-宫浦偶联，其中芳基酯的C（酰基）-O键的亲电体的作用，允许各种含酮的产品的合成。这与通过镍催化提供联芳基的类似酯的已知反应形成对比。这种机制分歧的根本原因进行了研究，通过DFT计算，和更亲电酰化偶联伙伴相比，酯的鲁棒性进行了分析。
The Suzuki-Miyaura coupling is among the most important C-C bond-forming reactions available due to its reliability, chemoselectivity, and diversity. Aryl halides and pseudohalides such as iodides, bromides, and triflates are traditionally used as the electrophilic coupling partner. The expansion of the reaction scope to nontraditional electrophiles is an ongoing challenge to enable an even greater number of useful products to be made from simple starting materials. Herein, we present how an NHC-based Pd catalyst can enable Suzuki-Miyaura coupling where the C(acyl)-O bond of aryl esters takes on the role of electrophile, allowing the synthesis of various ketone-containing products. This contrasts known reactions of similar esters that provide biaryls via nickel catalysis. The underlying cause of this mechanistic divergence is investigated by DFT calculations, and the robustness of esters compared to more electrophilic acylative coupling partners is analyzed.