Palladium‐Catalyzed Benzylic C(sp 3 )−H Carbonylative Arylation with Aryl Bromides
Palladium‐Catalyzed Benzylic C(sp 3 )−H Carbonylative Arylation with Aryl Bromides
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钯催化的苯甲基 C(sp 3 )·H 与芳基溴的羰基化芳基化反应
DOI：
10.1002/anie.202300073
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Walsh, Patrick J.
中科院分区：
文献类型：
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作者：
Hu, Bowen;Zhao, Haoqiang;Wu, Yu;Walsh, Patrick J.
以钯为催化剂，实现了多种弱酸性(二甲基亚砜中的pKa25-35)苄基和杂苯基C(Sp3)−H键与芳基溴化物的新型、选择性和高产率的羰基化芳基化反应。这一体系适用于一系列亲核试剂，以获得空间和电子上不同的α-芳基或α，α-二芳基酮，它们是生物活性化合物中普遍存在的亚结构。基于Josiphos SL-J001-1的钯催化剂被认为是最有效和选择性最高的催化剂，能够在1 的常压CO下与芳基溴化物进行羰基芳基化反应，从而提供酮产品，而不会形成直接偶联的副产物。(Josiphos)Pd(CO)2是催化剂的休眠状态。一项动力学研究表明，芳基溴化物的氧化加成是限制周转的步骤。还分离出了关键的催化中间体。
A novel, selective and high‐yielding palladium‐catalyzed carbonylative arylation of a variety of weakly acidic (pKa25–35 in DMSO) benzylic and heterobenzylic C(sp3)−H bonds with aryl bromides has been achieved. This system is applicable to a range of pro‐nucleophiles for access to sterically and electronically diverse α‐aryl or α,α‐diaryl ketones, which are ubiquitous substructures in biologically active compounds. The Josiphos SL‐J001‐1‐based palladium catalyst was identified as the most efficient and selective, enabling carbonylative arylation with aryl bromides under 1 atm CO to provide the ketone products without the formation of direct coupling byproducts. Additionally, (Josiphos)Pd(CO)2was identified as the catalyst resting state. A kinetic study suggests that the oxidative addition of aryl bromides is the turnover‐limiting step. Key catalytic intermediates were also isolated.