Arene‐Free Ruthenium(II/IV)‐Catalyzed Bifurcated Arylation for Oxidative C−H/C−H Functionalizations

Abstract

Experimental and computational studies provide detailed insight into the selectivity-and reactivity-controlling factors in bifurcated ruthenium-catalyzed direct CÀHa rylations and dehydrogenative CÀH/CÀHf unctionalizations. Thorough investigations revealed the importance of areneligand-free complexes for the formation of biscyclometalated intermediates within ar uthenium(II/IV/II) mechanistic manifold.

Reactivity-Controlling Factors in Carboxylate-Assisted C–H Activation under 4d and 3d Transition Metal Catalysis

“…27 In addition to cationic aryl acetamide-containing ruthenium(II) complexes, the C−H ruthenation process was further studied using the neutral ruthenium−benzoate 28 complex Ru-II as well as cyclometalated p-cymene-ligandfree ruthenium−phenylpyridine complex Ru-III (Figure 5). 29 Although significant differences could be observed for the C−H and Ru−C bond orders in the respective agostic intermediates B, the key C−H cleavage transition states TS(B−C) were in all three cases clearly located in the BIES rather than the CMD regime.…”

Photo‐Induced Ruthenium‐Catalyzed C−H Arylations at Ambient Temperature

“…During the recent decade,transition metal-catalyzed C À H functionalizations have emerged as ap owerful tool in molecular syntheses [1] with notable advances by ruthenium catalysis. [2] Particularly,C ÀHa rylations [3] have played an important role in material sciences,crop protection, and drug discovery. [4] Ruthenium-catalyzed CÀHarylations have hence been exploited for the synthesis of biologically active compounds,s uch as Anacetrapib,V alsartan, and Candesartan by Ouellet at Merck, [5] Ackermann, [6] and Seki, [7] respectively ( Figure 1a).…”

Highly Regioselective Direct C-H Arylation: Facile Construction of Symmetrical Dithienophthalimide-Based π -Conjugated Molecules for Optoelectronics

“…Organic π-conjugated molecules have been intensively explored over recent years for various potential applications, i.e., as active materials for organic light-emitting diodes (OLEDs) [1][2][3][4][5][6][7], organic photovoltaics [8][9][10], organic fieldeffect transistors [11][12][13][14], organic semiconductor lasers [15][16][17][18][19], theranostics [20][21][22], etc. The construction of organic conjugated molecules depends on the efficient formation of the carbon-carbon bond between two sp 2 carbons [23][24][25][26][27]. For this purpose, a variety of carbon-carbon cross-coupling reactions, such as Suzuki, Stille, Heck, and Kumada reactions, have thus been widely explored for the couplings of aryl halides with the toxic intermediates (organometallic/boride heteroaromatics) [28][29][30][31][32][33].…”