Electrostatically-directed Pd-catalysis in combination with C-H activation: site-selective coupling of remote chlorides with fluoroarenes and fluoroheteroarenes.
Electrostatically-directed Pd-catalysis in combination with C-H activation: site-selective coupling of remote chlorides with fluoroarenes and fluoroheteroarenes.
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DOI：
10.1039/d0sc00105h
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发表时间：
2020-02-18
期刊：
影响因子：
8.4
通讯作者：
Phipps RJ
中科院分区：
文献类型：
--
作者：
Golding WA;Phipps RJ
结合催化剂-底物非共价相互作用的系统正在成为解决远程功能化反应中位点选择性挑战的通用方法。鉴于使用铱、锰和铑等金属在这方面取得的成就，令人惊讶的是，尽管钯可以说是用于 C-H 活化的最通用的金属，但在包含钯催化的 C-H 活化步骤的反应中尚未利用非共价催化剂方向。在此，我们证明静电定向、位点选择性的 C-Cl 氧化加成与随后的 C-H 活化步骤兼容，通过协调的金属化去质子化型机制进行。这导致二氯芳烃与氟代芳烃和氟代杂芳烃发生位点选择性交叉偶联，选择性由催化剂结构控制。这项研究表明，Pd 催化的 C-H 活化可以与非共价引导的催化模式有效地结合使用，在这两个领域都具有重要意义。静电定向氧化加成与随后的 C-H 活化步骤兼容，从而实现远程氯化物与氟芳烃和氟杂芳烃的位点选择性偶联。
Systems incorporating catalyst–substrate non-covalent interactions are emerging as a versatile approach to address site-selectivity challenges in remote functionalization reactions. Given the achievements that have been made in this regard using metals such as iridium, manganese and rhodium, it is surprising that non-covalent catalyst direction has not been utilized in reactions incorporating palladium-catalyzed C–H activation steps, despite palladium being arguably the most versatile metal for C–H activation. Herein, we demonstrate that electrostatically directed, site-selective C–Cl oxidative addition is compatible with a subsequent C–H activation step, proceeding via a concerted metalation deprotonation-type mechanism. This results in site-selective cross-coupling of dichloroarenes with fluoroarenes and fluoroheteroarenes, with selectivity controlled by catalyst structure. This study demonstrates that Pd-catalyzed C–H activation can be used productively in combination with a non-covalently-directed mode of catalysis, with important implications in both fields. Electrostatically-directed oxidative addition is compatible with a subsequent C–H activation step, enabling site-selective coupling of remote chlorides with fluoroarenes and fluoroheteroarenes.
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DOI：
10.1002/anie.201708967
发表时间：
2017-10-16
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Davis HJ;Genov GR;Phipps RJ
通讯作者：
Phipps RJ
影响因子：
3.9
作者：
Bhattacharya, Trisha;Pimparkar, Sandeep;Maiti, Debabrata
通讯作者：
Maiti, Debabrata
影响因子：
4.3
作者：
Achar, Tapas Kumar;Ramakrishna, Kankanala;Maiti, Debabrata
通讯作者：
Maiti, Debabrata
影响因子：
15
作者：
Bastidas, Jose R. Montero;Oleskey, Thomas J.;Maleczka, Robert E., Jr.
通讯作者：
Maleczka, Robert E., Jr.
影响因子：
15
作者：
Chattopadhyay B;Dannatt JE;Andujar-De Sanctis IL;Gore KA;Maleczka RE Jr;Singleton DA;Smith MR 3rd
通讯作者：
Smith MR 3rd