RuH2(CO)(PPh3)3-catalyzed arylation of aromatic esters using arylboronates via C–H bond cleavages

Kitazawa, Kentaroh; Kotani, Masahiro; Kochi, Takuya; Langeloth, Michael; Kakiuchi, Fumitoshi

doi:10.1016/j.jorganchem.2010.01.022

Cited by 24 publications

(12 citation statements)

References 71 publications

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“…25b The observed rapid H/D exchanges in the reaction using the deuterium containing arylpyridines indicate that the C H bond cleavage occurs via oxidative addition and is not turnover limiting. Kinetic studies with 2 phenyl 3 picoline (19) and 17 under pseudo rst order conditions showed that the reaction rate appears to be independent of the concen-tration of 19 and is rst order with respect to the catalyst and 17. Two types of intermediates were structurally determined by NMR and single crystal X ray diffraction analyses.…”

Section: H Alkenylation With Alkenyl Esters Ethers Andmentioning

confidence: 99%

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Chelation-Assisted Catalytic C-C, C-Si, and C-Halogen Bond Formation by Substitution via the Cleavage of C(sp2)-H and C(sp3)-H Bonds

Kakiuchi

Kochi

2015

J. Syn. Org. Chem., Jpn.

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Catalytic, regioselective C H functionalizations have been extensively studied over the past two decades. In this account, we report our results on catalytic C C, C Si, and C halogen bond formation reactions by substitution via the cleavage of C H bonds. Catalytic arylation with arylboronates was developed and applied to the convenient synthesis of polycyclic aromatic hydrocarbons. Alkenylation reactions were also realized by the use of alkenylboronates and alkenyl esters. Various carbonyl containing substituents were introduced using carbamoyl chlorides, alkyl chloroformates, acyl chlorides, and cyclic alkenyl carbonates. C Si bonds were formed by reactions with hydrosilanes and vinylsilanes. C H halogenation reactions were achieved by a combination of C H bond cleavage and electrochemical oxidation and were applied to one pot arylation reactions using the Suzuki Miyaura coupling prodecure.

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Section: H Alkenylation With Alkenyl Esters Ethers Andmentioning

confidence: 99%

“…3). Various combinations of aromatic compounds such as aromatic ketones 18b esters, 19 and nitriles 20 with arylboronates can be used for the ruthenium catalyzed C H arylation.…”

Section: H Arylationmentioning

confidence: 99%

Chelation-Assisted Catalytic C-C, C-Si, and C-Halogen Bond Formation by Substitution via the Cleavage of C(sp2)-H and C(sp3)-H Bonds

Kakiuchi

Kochi

2015

J. Syn. Org. Chem., Jpn.

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“…[50] The keto moiety could be replaced with an ester as a directing group which also allowed the arylation of ortho C À H bonds in aromatic esters to proceed with arylboronate esters (Scheme 33). [51] Jun et al reported a similar Ru 3 (CO) 12 -catalysed arylation of aldimine C À H bonds with arylboronate esters utilising pyridyl moiety as a directing group (Scheme 34). [52] Under the reported conditions, the acetone cosolvent was proposed to act as a hydride acceptor in conjunction with a stoichiometric amount of methyl vinyl ketone (MVK) that also helped suppress reduction as well as 1,2-addition reactions on the aldimine substrates.…”

Section: Ru-catalysed C à H Couplingmentioning

confidence: 99%

“…The modified conditions also proved effective for the cross‐couplings of tert ‐butyl aryl ketones with vinylboronate esters (Scheme )48 and multiple arylations on large molecular frameworks such as anthraquinones49 and perylene bisimide (PBI) 50. The keto moiety could be replaced with an ester as a directing group which also allowed the arylation of ortho CH bonds in aromatic esters to proceed with arylboronate esters (Scheme ) 51. Jun et al.…”

Section: Ru‐catalysed Ch Couplingmentioning

confidence: 99%

Palladium‐Catalysed, Directed CH Coupling with Organometallics

Giri¹,

2014

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Transition metal (TM)-catalysed C À H coupling using organometallic reagents is developing into a distinct transformation area for the construction of carbon-carbon (C À C) bonds. Among different TMs (Ru, Rh, Pd, Co, Fe), complexes of palladium(II) are emerging as the most effective and versatile catalysts and have already asserted a proven track-record for the catalytic activation and coupling of unactivated sp 2 and sp 3 C À H bonds with sp 2 and sp 3 organometallic reagents. A majority of these TMcatalysed C À H coupling reactions utilise a hetero-A C H T U N G T R E N N U N G atom contained in substrates as a directing group. In the last decade, both traditional as well as non-traditional but synthetically useful functional groups have been extensively exploited as directing groups. Novel directing groups based on mechanistic understanding have also been designed to enhance the reactivity of Pd(II) catalysts towards C À H bonds. In addition, the unprecedented application of exogenous ligands to Pd(II)-catalysed C À H coupling is also on the rise, and this approach has already demonstrated an extraordinary level of success not only in breaking unactivated C À H bonds enantioselectively, but also in improving reactivity of catalysts towards these C À H bonds.

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“…We have been working on the efficient syntheses of PAH derivatives based on the ruthenium-catalyzed C-H/C-O arylation reactions developed in our group [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33]. In the presence of ruthenium carbonyl phosphine complexes, the reaction of aromatic ketones possessing C-H bonds or C-OR (R = alkyl) bonds with arylboronates provided C-H or C-O arylation products [21][22][23][24][25][26][27][28][29][30][31][32][33]. Anthraquinone was chosen as a convenient template for the PAH syntheses, because various anthraquinone derivatives possessing zero to four oxygen substituents at the orthopositions are readily available and the regioselective arylation at the positions of either C-H or C-O bonds provided a variety of multiarylated anthraquinone derivatives [16][17][18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

Terai¹,

Sato²,

Kochi³

et al. 2020

Beilstein J. Org. Chem.

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An efficient synthesis of tetrabenzo[a,d,j,m]coronene derivatives having alkyl and alkoxy substituents at the 3, 6, 13, and 16-positions was achieved based on the ruthenium-catalyzed coupling reactions of anthraquinone derivatives with arylboronates via C–H and C–O bond cleavage. The reaction sequence involving the arylation, carbonyl methylenation, and oxidative cyclization effectively provided various tetrabenzo[a,d,j,m]coronenes in short steps from readily available starting materials. Tetrabenzo[a,d,j,m]coronenes possessing two different types of substituents were obtained selectively by sequential chemoselective C–O arylation and C–H arylation. The 1H NMR spectra of the tetrabenzo[a,d,j,m]coronene product indicated its self-assembling behavior in CDCl3.

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RuH2(CO)(PPh3)3-catalyzed arylation of aromatic esters using arylboronates via C–H bond cleavages

Cited by 24 publications

References 71 publications

Chelation-Assisted Catalytic C-C, C-Si, and C-Halogen Bond Formation by Substitution via the Cleavage of C(sp<sup>2</sup>)-H and C(sp<sup>3</sup>)-H Bonds

Chelation-Assisted Catalytic C-C, C-Si, and C-Halogen Bond Formation by Substitution via the Cleavage of C(sp<sup>2</sup>)-H and C(sp<sup>3</sup>)-H Bonds

Palladium‐Catalysed, Directed CH Coupling with Organometallics

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

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