Ruthenium-Catalyzed Carbonylation at Ortho C−H Bonds in Aromatic Amides Leading to Phthalimides: C−H Bond Activation Utilizing a Bidentate System

Abstract

A new type of carbonylation of the ortho C-H bonds in aromatic amides 1, in which the pyridin-2-ylmethylamino moiety functions as a bidentate directing group, can be achieved. The presence of ethylene as a hydrogen acceptor and also of H(2)O, probably for the generation of an active catalytic species, is required. A wide variety of functional groups, including methoxy, amino, ester, ketone, cyano, chloro, and even bromo substituents, can be substituted for aromatic amides. The complex 9 was isolated by the stoichiometric reaction of 1b and Ru(3)(CO)(12), in which 1b binds to one Ru atom in the expected N,N fashion and the carbonyl oxygen binds to the other Ru atom as an O donor.

Copper‐Mediated ortho‐Nitration of Arene and Heteroarene CH Bonds Assisted by an 8‐Aminoquinoline Directing Group

“…[9] Since the pioneering work of Daugulis and co-workers on the introduction of picolinic acid and 8-aminoquinoline auxiliaries as removable directing groups, [10] extensive research efforts have been devoted to the development of methods for the palladium-catalyzed arylation, alkylation, alkenylation, alkynylation, alkoxylation, borylation, silylation and intramolecular amination of sp 2 and sp 3 C À H bonds. [10,11] Additionally, investigations of these bidentate auxiliaries in C À H bond functionalization based on relatively cheaper metal catalysts such as iron, [12] cobalt, [13] nickel, [14] and ruthenium [15] have also been carried out by several groups. As for the use of Cu salts, Daugulis and co-workers recently discovered the aminoquinoline-and picolinamide-directed, copper-catalyzed sulfenylation, amination, fluorination and etherification of arene and heteroarene C À H bonds [16] while Miura and co-workers discovered the copper-mediated coupling of benzoic acid derivatives and 1,3-azoles with the aid of an 8-aminoquinoline-based double N,N-coordination strategy.…”

“…Extensive screening studies showed that the efficiency of the reaction could be significantly affected by the choice of the base used and K 2 HPO 4 was determined to be the best base for this reaction (Table 1, entries 2-7). It is important to note that the selectivity [15][16][17][18]. When the reaction was conducted in DMF, much to our surprise, the selectivity of mononitrated product 2a vs. dinitrated product 3a was reversed and they are isolated in a 1:2 ratio with a 46% combined yield (Table 1, entry 19).…”

Construction of Heterocycle Scaffolds via Transition Metal‐ Catalyzed sp2 CH Functionalization

“…Chatanis group [25] reported a Ru 3 (CO) 12 (5 mol%) catalyzed synthesis of phthalimides via a C À H activation/cyclocarbonylation sequence using a bidentate system (Scheme 21). Me, OMe, NMe 2 , COOMe, C(O)CH 3 , CN, Cl, Br, OCF 3 groups are tolerated in this transformation.…”

The Use of a Rhodium Catalyst/8-Aminoquinoline Directing Group in the C-H Alkylation of Aromatic Amides with Alkenes: Possible Generation of a Carbene Intermediate from an Alkene

“…In 2009, we reported the first examples of Ru(0)-catalyzed reactions in which aromatic amides that contain 2-pyridinylmethylamine as the N,N¤-bidentate directing group in which C-H carbonylation resulted in the production of phthalimide derivatives. 25 Remarkably, this newly developed system was also successfully applied to the carbonylation of unactivated C(sp 3 )-H bonds in aliphatic amides. 26 In subsequent studies, we explored the use of Ni(0), 27 Ru(II), 28 Ni(II), 29 and Rh(I) 30 complexes as catalysts in C-H functionalizations using a bidentate-chelation system.…”