Nickel-Catalyzed Ortho-Arylation of Unactivated (Hetero)aryl C–H Bonds with Arylsilanes Using a Removable Auxiliary

Abstract

Ni(II)-catalyzed ortho-arylation of aromatic and heteroaromatic carboxamides with triethoxy(aryl)silanes assisted by a removable bidentate auxiliary is reported. This transformation features a broad substrate scope, good functional group tolerance, and compatibility with heterocyclic substrates. Compared to the well-established Ni(II)-catalyzed C-H arylation with ArX or aryliodonium salts via oxidative addition, this reaction proceeded via a fluoride-promoted transmetalation.

Cobalt‐Catalyzed Hiyama‐Type C−H Activation with Arylsiloxanes: Versatile Access to Highly ortho‐Decorated Biaryls

“…Nonetheless, the challenge associated with the use of less reactive silicon‐based arylating reagents was successfully addressed, albeit with the aid of noble 4d metal catalysts, such as palladium, rhodium, iridium and ruthenium . In contrast, nickel Hiyama‐type catalysis was elegantly developed by Miura and Shi, although required drastic reaction temperatures of 150 °C, while not being applicable towards challenging di‐ or even tri‐ ortho ‐substitution patterns. In sharp contrast, within our program on sustainable C−H activation, we have now devised the first cobalt‐catalyzed C−H arylation with silicon‐based arylating agents.…”

“…[9] Unfortunately,t his unique stabilityd irectly translates into as ignificantlyr educed transmetalation reactivity.N onetheless,t he challenge associated with the use of less reactive silicon-baseda rylating reagents was successfully addressed, albeit with the aid of noble 4d metalc atalysts, such as palladium, [10,11] rhodium, [12] iridium [13] and ruthenium. [14] In contrast, nickel Hiyama-type catalysis was elegantly developed by Miura [15] andS hi, [16] although required drastic reaction temperatureso f1 50 8C, while not being applicable towards challenging di-or even tri-ortho-substitution patterns.I ns harpc ontrast, within our programo ns ustainable CÀHa ctivation, [17] we have now devised the first cobalt-catalyzed CÀHa rylation with silicon-based arylating agents. Notable features of our finding include (a) unprecedented cobaltcatalyzed CÀHa rylations with aryl siloxanes,( b) rather mild reactiontemperatures, (c) the use of biomass-derived g-valerolactone (GVL) [18] solvent, and (d) mild Grignard-free conditions.…”

Cross-Coupling of Directed C-H and Organometallic Reagents for C-C Bond Formation

“…当把反应底物由苯甲酰胺变成 N-乙酰苯胺时, 反 应也能够很好地进行 [48] [51] , 但均使用 Pd、Rh 等贵金属作为催化剂. 2016 年, Shi 课题 [52] 组使用廉价的 Ni 作催化剂, 实现了底物 邻位 C-H 键的芳基化反应(Eq. 21).…”

C–H Functionalization of Aromatic Amides

“…Among the coupling agents used in the reaction, arylsilanes have the advantages of low toxicity and safe operation. In 2016, the Shi group reported for the first time the C–H arylation of aromatic amides with arylsilanes to afford diaryl compounds catalyzed by the first row transition metal Ni(II) (Scheme ) . The reaction mechanism proposed by the authors is as follows: benzamide coordinates with Ni(II) and activates the ortho ‐C−H bond to obtain intermediate A , which is then oxidized to intermediate B under the action of oxidant.…”