Transition-Metal-Catalyzed Carbon-Carbon Bond Formation via Carbon-Hydrogen Bond Cleavage

Kakiuchi, Fumitoshi; Kochi, Takuya

doi:10.1055/s-2008-1067256

Cited by 771 publications

(117 citation statements)

References 66 publications

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“…Under these conditions, the excess of benzofurazan can be decreased up to 1.15 equivalents, as the desired product 1 was isolated in 89% yield (Table 1, entry 10). Then, we employed greener solvents than DMA such as cyclopentylmethyl ether, 1-pentanol or diethylcarbonate, [15] but no reaction occurred (Table 1, entries [11][12][13]. No reaction occurred when 4-chlorobenzonitrile was used as aryl source (Table 1, entry 14).…”

Section: Resultsmentioning

confidence: 99%

“…[8] Since the discovery by Nakamura [9] and Otha [10] of the Pd-catalyzed C-H bond arylation of heteroarenes using aryl halides, this technology has emerged as one of the most powerful method for the formation of C-C bonds for the access to a wide variety of arylated heterocycles as no prefunctionalization is required. [11] However, examples of palladium-catalyzed non-directed C-H bond arylation of 6-membered rings remains scarce. [12] Recent examples on the arylation of activated benzothiadiazole via C-H bond activation have been reported using palladium catalysis.…”

Section: Introductionmentioning

confidence: 99%

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Palladium‐Catalyzed Regioselective Direct Arylation of Benzofurazans at the C‐4 Position

et al. 2017

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Abstract. The palladium-catalyzed direct arylation of benzofurazans with aryl bromides to access 4-arylbenzofurazans proceeds in moderate-to-high yields using phosphine-free palladium acetate as the catalyst and potassium acetate as an inexpensive base. A wide variety of (hetero)aryl bromides, including bromopyridine and bromothiophene derivatives has been successfully employed.Palladium-catalyzed one-pot C4,C7-diarylation of benzofurazane was also described using a larger amount of aryl bromide. Moreover, the derivatization of 4-arylbenzofurazans into 4-arylquinaxolines is also reported.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Regioselective Direct Arylation of Benzofurazans at the C‐4 Position

et al. 2017

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“…[167][168][169][170][171][172][173] The reaction of 12b with 2-methylthiophene (30) was carried out with SiNA-Pd (0.3 mol%) and CsOAc in DMF, then the reaction proceeded to give 2-methyl-5-phenylthiophene (31) in 80% yield. [174][175][176][177] The coupling of 12b with an indole (32) also proceeded under similar conditions to give the corresponding indole 33 in 63% yield.…”

Section: )mentioning

confidence: 99%

Development of Batch and Flow Immobilized Catalytic Systems with High Catalytic Activity and Reusability

Yamada

2017

CHEMICAL & PHARMACEUTICAL BULLETIN

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My mission in catalysis research is to develop highly active and reusable supported catalytic systems in terms of fundamental chemistry and industrial application. For this purpose, I developed three types of highly active and reusable supported catalytic systems. The first type involves polymeric base-supported metal catalysts: Novel polymeric imidazole-Pd and Cu complexes were developed that worked at the mol ppm level for a variety of organic transformations. The second involves catalytic membrane-installed microflow reactors: Membranous polymeric palladium and copper complex/nanoparticle catalysts were installed at the center of a microtube to produce novel catalytic membrane-immobilized flow microreactor devices. These catalytic devices mediated a variety of organic transformations to afford the corresponding products in high yield within 1-38 s. The third is a silicon nanowire array-immobilized palladium nanoparticle catalyst. This device promoted a variety of organic transformations as a heterogeneous catalyst. The Mizoroki-Heck reaction proceeded with 280 mol ppb (0.000028 mol%) of the catalyst, affording the corresponding products in high yield.

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“…2,3 The importance of such processes is also apparent from the significance of catalytic C H bond functionalization in chemical synthesis. 4 Indeed, the quest for such methods has been the driving force behind enormous efforts in the synthetic community including our group, culminating in a wealth of useful catalytic systems for reactions assembling arenes through C H bond functionalization. 2 The C H bond arylations of arenes can be formally classifi ed into the following three types; (i) C H/C X biaryl coupling, (ii) C H/C M biaryl coupling, and (iii) C H/C H biaryl coupling.…”

Section: Introductionmentioning

confidence: 99%

Toward Ideal Arene Assembly: Catalytic C-H Bond Arylation of Aromatic Compounds

Itami

2010

J. Synth. Org. Chem. Jpn.

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Abstract:In this account, the early stages of our campaign (2006 2009) to develop catalysts able to realize ideal arene assembly through catalytic C H bond arylation of aromatic compounds are described. New Rh, Ir, and Ni catalysts have been developed for the C H bond arylation of heteroarenes with haloarenes. It was also found that Cu(OCOCF 3 ) 2 can promote the C H bond arylation of electron rich arenes with aryl boronic acids. During these studies, we accidentally discovered that KOt Bu alone can promote the C H bond arylation of electron defi cient nitrogen heterocycles with haloarenes. Through a sequence of three consecutive bond selective C H arylations, a programmed synthesis of tetraarylthiophenes has been established. During this study, we discovered metal and ligand controlled regiodivergency in C H bond arylation. Scheme 1. Arene assembling reactions through C H bond functionali zation.J. Synth. Org. Chem., Jpn. 1132 Rhodium Catalyzed C H/C X Biaryl CouplingOur initial scenario for realizing an effi cient transition metal catalyzed biaryl coupling of arenes with haloarenes (C H/C X biaryl coupling) has been the redox catalysis shown in Scheme 3. 8 This involves (i) oxidative addition of haloarene (Ar X) to transition metal complex (M), (ii) electrophilic metalation of arene (Ar H) with thus formed Ar M X giving diarylmetal species, and (iii) reductive elimination of biaryl product (Ar Ar) with the regeneration of catalyst M. We envisaged that the use of electron withdrawing neutral ligand would lead to a distinct nucleophile electrophile interaction between an arene (Ar H) and Ar M X species, thereby promoting electrophilic arene metalation. In addition, we also expected such a ligand to facilitate the product forming reductive elimination step. This mechanistic blueprint means our designed C H/C X biaryl coupling should best be described as a Friedel Crafts aromatic arylation reaction.In order to fi nd an as yet unexplored catalyst of this kind, we took a very distinct and unconventional approach. Rather than screening various ligands for a transition metal, we screened transition metals by fi xing the ligand as P[OCH(CF 3 ) 2 ] 3 which is known to be one of the most electron withdrawing neutral ligands.9 After extensive screening, we were able to identify that Rh 10 is a central metal of choice, able to realize our concept, and that RhCl(CO){P[OCH(CF 3 ) 2 ] 3 } 2 (1) is a bench stable catalyst precursor (Scheme 3). 8 The complex 1 can be prepared quantitatively by mixing [RhCl(CO) 2 ] 2 and P[OCH(CF 3 ) 2 ] 3 in toluene. A notable feature of this complex is its outstanding stability to air and moisture in the solid state. Virtually no decomposition of 1 has been detected after extended ( 10 months) exposure to air. The X ray crystal structure of 1 indicates that this may be partly due to effective shielding of the Rh atom by two bulky phosphite ligands (Scheme 3).Rhodium complex 1, with the assistance of silver carbonate, catalyzed the C H/C X biaryl coupling of electron rich heteroarenes and iod...

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Transition-Metal-Catalyzed Carbon-Carbon Bond Formation via Carbon-Hydrogen Bond Cleavage

Cited by 771 publications

References 66 publications

Palladium‐Catalyzed Regioselective Direct Arylation of Benzofurazans at the C‐4 Position

Palladium‐Catalyzed Regioselective Direct Arylation of Benzofurazans at the C‐4 Position

Development of Batch and Flow Immobilized Catalytic Systems with High Catalytic Activity and Reusability

Toward Ideal Arene Assembly: Catalytic C-H Bond Arylation of Aromatic Compounds

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