164173-00-6Relevant articles and documents
Iridium-catalyzed Decarbonylative Coupling of Acyl Fluorides with Arenes and Heteroarenes via C-H Activation
Sakurai, Shun,Yoshida, Tomoki,Tobisu, Mamoru
, p. 94 - 97 (2019)
The first method for decarbonylative direct arylation using acyl fluorides is reported. This reaction proceeds, only when acyl fluorides are used, and other acyl halides cannot be used. The reaction can be applied to the direct arylation of a variety of substrates, including xylene, quinoline, and benzothiophene.
The site-selectivity and mechanism of Pd-catalyzed C(sp2)-H arylation of simple arenes
Kim, Daeun,Choi, Geunho,Kim, Weonjeong,Kim, Dongwook,Kang, Youn K.,Hong, Soon Hyeok
, p. 363 - 373 (2021/01/14)
Control over site-selectivity is a critical challenge for practical application of catalytic C-H functionalization reactions in organic synthesis. Despite the seminal breakthrough of the Pd-catalyzed C(sp2)-H arylation of simple arenes via a concerted metalation-deprotonation (CMD) pathway in 2006, understanding the site-selectivity of the reaction still remains elusive. Here, we have comprehensively investigated the scope, site-selectivity, and mechanism of the Pd-catalyzed direct C-H arylation reaction of simple arenes. Counterintuitively, electron-rich arenes preferably undergo meta-arylation without the need for a specifically designed directing group, whereas electron-deficient arenes bearing fluoro or cyano groups exhibit high ortho-selectivity and electron-deficient arenes bearing bulky electron-withdrawing groups favor the meta-product. Comprehensive mechanistic investigations through a combination of kinetic measurements and stoichiometric experiments using arylpalladium complexes have revealed that the Pd-based catalytic system works via a cooperative bimetallic mechanism, not the originally proposed monometallic CMD mechanism, regardless of the presence of a strongly coordinating L-type ligand. Notably, the transmetalation step, which is influenced by a potassium cation, is suggested as the selectivity-determining step.
Ni-Catalyzed Cross-Coupling of Dimethyl Aryl Amines with Arylboronic Esters under Reductive Conditions
Cao, Zhi-Chao,Xie, Si-Jun,Fang, Huayi,Shi, Zhang-Jie
supporting information, p. 13575 - 13579 (2018/10/24)
Herein, we reported a successful Suzuki-Miyaura coupling of dimethyl aryl amines to forge biaryl skeleton via Ni catalysis in the absence of directing groups and preactivation. This transformation proceeded with high efficiency in the presence of magnesium. Preliminary mechanism studies demonstrated dual roles of magnesium: (i) a reductant that reduced Ni(II) species to active Ni(I) catalyst; (ii) a unique promoter that facilitated the Ni(I)/Ni(III) catalytic cycle.
