論文 - 河内　卓彌

Palladium-Catalyzed Electrochemical Iodination of 1-Arylpyridine N-Oxides

Zhou H., Miyasaka M., Wang Y.H., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  2023年

ISSN  00223263

　概要を見る

The palladium-catalyzed C-H iodination of 1-arylpyridine N-oxides proceeded under electrochemical oxidation conditions using I2 as an iodine source. The reaction of isoquinoline N-oxides possessing various para- or meta-substituted aryl groups at the 1-position proceeded to give the corresponding iodination products. Electron-donating groups on the aryl group facilitated the reaction to give relatively high yields of the product. The reaction was also found to be applicable to 2-aryl-3-picoline N-oxides.

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Conformational Isomerization as a Process to Determine Selectivity over Reaction Pathways: Effect of Alkene Rotation in Chain Walking via Cis Alkene Intermediates

Muto K., Hatanaka M., Kakiuchi F., Kochi T.

Journal of Organic Chemistry （Journal of Organic Chemistry）  89 （ 7 ） 4712 - 4721 2024年04月

ISSN  00223263

　概要を見る

In organic reactions, bond-forming and bond-cleaving processes are generally considered to be more important than other processes such as conformational isomerization. We report herein an example where a conformational isomerization process, propeller-like alkene rotation, is considered to determine the selectivity over the reaction pathways. The transition state with the highest energy barrier in some alkylpalladium isomerization (chain walking) events was theoretically indicated to correspond to alkene rotation, while transition states for bond-cleaving β-hydride elimination and bond-forming migratory insertion were not even observed. It was also suggested both theoretically and experimentally that the palladium chain walking over internal carbons in alkyl chains proceeds via cis alkene intermediates rather than thermodynamically more stable trans alkene intermediates, due to their relative difficulty to undergo alkene rotation.

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Off/on Switching of Electric Current as a Strategy for One-Pot Synthesis of Bromoarylpyridines by Cross-Coupling/ C−H Bromination

Hirota Y., Fujie T., Kochi T., Kakiuchi F.

Israel Journal of Chemistry （Israel Journal of Chemistry）  64 （ 1-2 ）  2024年01月

ISSN  00212148

　概要を見る

An “OFF/ON” electric current switching protocol was developed as a new strategy for one-pot organic synthesis. Suzuki-Miyaura coupling of 2-bromopyridines with arylboronic acids in an electrochemical cell was performed without applying an electric current, and subsequently, the Pd-catalyzed electrochemical C−H bromination was conducted using the already-present Pd catalyst to obtain 2-(2-bromoaryl)pyridines as products. The one-pot synthesis of bromoarenes can also be achieved without adding an external Br source in the second step. Furthermore, an OFF/ON/OFF two-times switching protocol also realized the formation of an N-containing teraryl derivative.

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Rhodium-Catalyzed β-Acylalkylation of Allylbenzene Derivatives with Allyl Alcohols via C-C Bond Cleavage

Ishikawa S., Togashi R., Ueda R., Onodera S., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  88 （ 5 ） 3313 - 3320 2023年03月

ISSN  00223263

　概要を見る

We report here a deallylative β-acylalkylation reaction of allylbenzene derivatives with allyl alcohols in the presence of Cp*Rh catalysts. Allylbenzenes possessing pyridyl and pyrazolyl directing groups were converted to β-aryl ketones via the cleavage of C(aryl)-C(allyl) bonds. Synthesis of a quinoline derivative from a β-aryl ketone product bearing a pyrazolyl group was also achieved.

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Palladium-Catalyzed Hydroboration/Cyclization of 1,n-Dienes

Kanno S., Kakiuchi F., Kochi T.

Journal of Organic Chemistry （Journal of Organic Chemistry）  88 （ 4 ） 2621 - 2630 2023年02月

ISSN  00223263

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While the hydroboration of alkenes is well established, the corresponding cyclization reaction of dienes remains challenging. Here, we report a new method for hydroboration/cyclization applicable to various 1,n-dienes and hydroboranes. The method features the direct synthesis of borylalkyl cyclopentanes from common 1,6-dienes, which is highlighted by syntheses of elaborated pyrrolidine cores from easily accessible diallylamines. Notably, 1,n-dienes (n > 6) also undergo five-membered ring formation, offering “remote” hydroboration/cyclization that would be otherwise difficult to achieve.

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Iron-Catalyzed Regio- and Stereoselective C-H Alkenylation of Pivalophenone Derivatives with Unsymmetric Internal Alkynes

Kitazawa Y., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  88 （ 3 ） 1890 - 1897 2023年02月

ISSN  00223263

　概要を見る

Here we report an ortho-C-H alkenylation of aromatic ketones with unsymmetric internal alkynes catalyzed by an iron phosphine complex, Fe(PMe3)4. The use of a catalytic amount of PtBu3 as an additive was found to improve the product yields. The alkenylation proceeds regio- and stereoselectively to give the corresponding styrene derivatives.

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Desymmetrization of prochiral methylenes by asymmetric chain-walking cyclization using bioxazoline palladium catalysts

Shigekane M., Arai T., Tamura M., Uchida T., Kakiuchi F., Kochi T.

Tetrahedron Letters （Tetrahedron Letters）  114 2023年01月

ISSN  00404039

　概要を見る

We present here that the use of bioxazoline ligands improved the enantioselectivity of the palladium-catalyzed chain-walking cycloisomerization of 1,n-dienes. The new system was applied to the asymmetric chain-walking cycloisomerization of a variety of 1,n-dienes as well as asymmetric hydrosilylation/cyclization of a 1,8-diene.

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Palladium-Catalyzed Remote Diborylative Cyclization of Dienes with Diborons via Chain Walking

Kanno S., Kakiuchi F., Kochi T.

Journal of the American Chemical Society （Journal of the American Chemical Society）  143 （ 46 ） 19275 - 19281 2021年11月

ISSN  00027863

　概要を見る

A novel method for catalytic remote bismetalation of alkene substrates by the addition of dimetal reagents is accomplished by using chain walking. In the presence of a palladium catalyst, the reaction of various 1,n-dienes and diborons were converted into cyclopentane derivatives with two boryl groups at remote positions via facile regioselective transformation of an unactivated sp3 C-H bond to a C-B bond. Sequential construction of three distant bonds, which is difficult to achieve by any method, was accomplished for the reactions of 1,n-dienes (n ≥ 7).

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Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β-Acetoxy Elimination

Muto K., Kumagai T., Kakiuchi F., Kochi T.

Angewandte Chemie - International Edition （Angewandte Chemie - International Edition）  60 （ 46 ） 24500 - 24504 2021年11月

ISSN  14337851

　概要を見る

Palladium-catalyzed remote arylative substitution was achieved for the reaction of arylboronic acids with alkenes possessing a distant acetoxy group to provide arylation products having an alkene moiety at the remote position. The use of β-acetoxy elimination as a key step in the catalytic cycle allowed for regioselective formation of unstabilized alkenes after chain walking. This reaction was applicable to various arylboronic acids as well as alkene substrates.

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Anti-Markovnikov Addition of Anilines to Aliphatic Terminal Alkynes Catalyzed by an 8-Quinolinolato Rhodium Complex

Morimoto Y., Kochi T., Kakiuchi F.

Helvetica Chimica Acta （Helvetica Chimica Acta）  104 （ 10 ）  2021年10月

ISSN  0018019X

　概要を見る

Anti-Markovnikov addition of anilines to aliphatic terminal alkynes proceeded using an 8-quinolinolato rhodium/phosphine catalyst system. The use of a strong organic base, 1,1,3,3,–tetramethylguanidine, in the catalyst system enabled the formation of the aldimine products. Substrates with various functional groups including polar groups such as a phenolic hydroxy group are applicable to the hydroamination.

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Rhodium-Catalyzed Anti-Markovnikov Hydroamination of Aliphatic and Aromatic Terminal Alkynes with Aliphatic Primary Amines

Morimoto Y., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  86 （ 18 ） 13143 - 13152 2021年09月

ISSN  00223263

　概要を見る

Anti-Markovnikov hydroamination of both aliphatic and aromatic terminal alkynes with primary amines was achieved using an 8-quinolinolato rhodium catalyst to form aldimines and enamines in high yields. This catalytic system realized high functional group tolerance including hydroxy, bromo, cyano, and thioester groups.

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Deuterium-Labeling Studies on the C-H/Olefin Coupling of Aromatic Ketones Catalyzed by Fe(PMe <inf>3</inf>) <inf>4</inf>

Kimura N., Katta S., Kitazawa Y., Kochi T., Kakiuchi F.

Synthesis (Germany) （Synthesis (Germany)）  53 （ 18 ） 3383 - 3389 2021年09月

ISSN  00397881

　概要を見る

Deuterium-labeling experiments were performed for the Fe(PMe 3) 4-catalyzed C-H/olefin coupling using a deuterium-labeled aromatic ketone with various alkenes. While the reactions with a variety of alkenes provided the linear alkylation products formed via 1,2-insertion of alkene into an Fe-H bond, the reversible 2,1-insertion proceeded during the reaction highly depends on the choice of the alkene. No H/D scrambling resulting from 2,1-insertion/β-elimination was detected for the reactions with a vinylsilane and N -vinylcarbazole, but the reactions with styrenes are considered to involve rapid 2,1-insertion/ β-elimination processes to cause significant levels of H/D scrambling.

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2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis

Morimoto Y., Hamada M., Takano S., Mochizuki K., Kochi T., Kakiuchi F.

Organic Letters （Organic Letters）  23 （ 10 ） 3803 - 3808 2021年05月

ISSN  15237060

　概要を見る

Both 2:1 and 1:1 couplings of alkylacetylenes with secondary amines were achieved using 8-quinolinolato rhodium catalysts and CsF. The 2:1/1:1 selectivity was switched by choosing the reaction solvent. In DMA, an unprecedented 2:1 coupling reaction of alkylacetylenes with amines proceeded to give 2-aminodiene products. One-pot 2:1 coupling/reduction provided rapid access to various allylamines, while one-pot coupling/hydrolysis gave enones as products. In toluene, anti-Markovnikov hydroamination occurred under relatively mild conditions to give 1:1 coupling products.

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Iron-Catalyzed Ortho C-H Homoallylation of Aromatic Ketones with Methylenecyclopropanes

Kimura N., Katta S., Kitazawa Y., Kochi T., Kakiuchi F.

Journal of the American Chemical Society （Journal of the American Chemical Society）  143 （ 12 ） 4543 - 4549 2021年03月

ISSN  00027863

　概要を見る

We report here a C-H homoallylation reaction of aromatic ketones with methylenecyclopropanes (MCPs) only using a catalytic amount of Fe(PMe3)4. A variety of aromatic ketones and MCPs are applicable to the reaction to form ortho-homoallylated aromatic ketones selectively via regioselective scission of the three-membered rings. The homoallylated products are amenable to further elaborations, providing functionalized 1,2-dihydronaphthalenes.

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Carbon–Carbon Bond Formation via Catalytically Generated Aminocarbene Complexes: Rhodium-Catalyzed Hydroaminative Cyclization of Enynes with Secondary Amines

Takano S., Shiomi R., Morimoto Y., Kochi T., Kakiuchi F.

Angewandte Chemie - International Edition （Angewandte Chemie - International Edition）  59 （ 29 ） 11754 - 11757 2020年07月

ISSN  14337851

　概要を見る

We report a hydroaminative cyclization of enynes using phosphine-quinolinolato rhodium catalysts. The hydroaminative cyclization of 2-vinylphenylacetylene derivatives with secondary amines gives 2-aminoindenes in good yields. The reaction is considered to proceed through carbon–carbon bond formation on a catalytically generated aminocarbene ligand.

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Catalytic, Directed C-C Bond Functionalization of Styrenes

Onodera S., Togashi R., Ishikawa S., Kochi T., Kakiuchi F.

Journal of the American Chemical Society （Journal of the American Chemical Society）  142 （ 16 ） 7345 - 7349 2020年04月

ISSN  00027863

　概要を見る

A method for catalytic conversion of C(aryl)-C(alkenyl) bonds in styrene derivatives to new C-C bonds is developed. In the presence of a rhodium catalyst, the alkenyl groups of styrenes bearing a pyrazolyl directing group were efficiently converted to other carbon substituents upon reacting with various alkenes including styrenes, aliphatic alkenes, and allyl alcohols. It is also indicated that the C-C bond cleavage proceeded via a hydrometalation/β-carbon elimination pathway.

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

Terai S., Sato Y., Kochi T., Kakiuchi F.

Beilstein Journal of Organic Chemistry （Beilstein Journal of Organic Chemistry）  16   544 - 550 2020年03月

ISSN  1860-5397

　概要を見る

An efficient synthesis of tetrabenzo[a,d,j,m]coronene derivatives having alkyl and alkoxy substituents at the 3, 6, 13, and 16-posi-tions 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. Tetra-benzo[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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In Situ Generation of Ruthenium Carbonyl Phosphine Complexes as a Versatile Method for the Development of Enantioselective C−O Bond Arylation

Kondo H., Kochi T., Kakiuchi F.

Chemistry - A European Journal （Chemistry - A European Journal）  26 （ 8 ） 1737 - 1741 2020年02月

ISSN  09476539

　概要を見る

We report here a method for in situ generation of various ruthenium carbonyl phosphine catalysts for arylation via cleavage of inert aromatic carbon–oxygen bonds. The use of catalyst systems consisting of [RuCl2(CO)(p-cymene)], CsF, styrene, and phosphines enabled facile screening of phosphine ligands. Asymmetric C–O arylation was also achieved for atropo-enantioselective biaryl synthesis using a chiral monodentate phosphine ligand.

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Selective Monoarylation of Aromatic Ketones via C-H Bond Cleavage by Trialkylphosphine Ruthenium Catalysts

Suzuki I., Kondo H., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  84 （ 20 ） 12975 - 12982 2019年

ISSN  00223263

　概要を見る

© 2019 American Chemical Society. A catalyst system consisting of RuHCl(CO)(PiPr3)2, CsF, and a styrene derivative was found to be applicable to selective monoarylation of aromatic ketones via ortho C-H bond cleavage. The reaction of 2′-methoxyacetophenone with arylboronates gave C-H arylation products without cleaving the ortho C-O bond. Acetophenone was also converted to monoarylation products with high selectivity. Cyclohexanone was found to be an effective solvent for the C-H arylation using the catalyst system.

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Iron-Catalyzed Ortho-Selective C−H Alkylation of Aromatic Ketones with N-Alkenylindoles and Partial Indolylation via 1,4-Iron Migration

Kimura N., Kochi T., Kakiuchi F.

Asian Journal of Organic Chemistry （Asian Journal of Organic Chemistry）  8 （ 7 ） 1115 - 1117 2019年07月

ISSN  21935807

　概要を見る

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim An ortho-selective C−H alkylation of aromatic ketones with N-alkenylindoles proceeded in the presence of just a Fe(PMe3)4 catalyst. In addition, C−H indolylation products, which are considered to be formed via 1,4-iron migration, were also observed as minor products.

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Synthesis of N-Arylpyrazoles by Palladium-Catalyzed Coupling of Aryl Triflates with Pyrazole Derivatives

Onodera S., Kochi T., Kakiuchi F.

Journal of Organic Chemistry （Journal of Organic Chemistry）  84 （ 10 ） 6508 - 6515 2019年05月

ISSN  00223263

　概要を見る

© 2019 American Chemical Society. A method for the synthesis of N-arylpyrazoles by palladium-catalyzed coupling of aryl triflates with pyrazole derivatives is described. Using tBuBrettPhos as a ligand, the palladium-catalyzed C-N coupling of a variety of aryl triflates including ortho-substituted ones with pyrazole derivatives proceeded efficiently to give N-arylpyrazole products in high yields. 3-Trimethylsilylpyrazole was found to be an excellent pyrazole substrate for the coupling, and the corresponding product, 1-aryl-3-trimethylsilylpyrazole, also served as a great template for the syntheses of N-arylpyrazole derivatives, as demonstrated by regioselective halogenation at the 3-, 4-, and 5-positions of the pyrazole ring.

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Metal-Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium-Catalyzed Hydrosilylation/Cyclization of 1,n-Dienes by Chain Walking

Kochi T., Ichinose K., Shigekane M., Hamasaki T., Kakiuchi F.

Angewandte Chemie - International Edition （Angewandte Chemie - International Edition）  58 （ 16 ） 5261 - 5265 2019年04月

ISSN  14337851

　概要を見る

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Sequential formation of distant bonds in organic molecules was achieved for the palladium-catalyzed hydrosilylation/cyclization of various 1,n-dienes by chain walking of the metal catalyst. The reaction was applicable to various 1,n-dienes, including a 1,13-diene, to form a cyclopentane ring as well as a carbon–silicon bond at a remote site. The use of “nondissociative” chain walking provides a fascinating strategy in organic synthesis to functionalize distant parts of organic molecules, in a particular order, within a catalytic cycle by effectively moving the reactive center from a remote position.

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Selective Long-Distance Isomerization of Terminal Alkenes via Nondissociative Chain Walking

Yamasaki Y., Kumagai T., Kanno S., Kakiuchi F., Kochi T.

Journal of Organic Chemistry （Journal of Organic Chemistry）  83 （ 16 ） 9322 - 9333 2018年08月

ISSN  00223263

　概要を見る

© 2018 American Chemical Society. Selective long-distance isomerization of terminal alkenes to silyl enol ethers proceeded via nondissociative chain walking using phenanthroline palladium catalysts. Notable features achieved taking advantage of the nondissociative chain walking mechanism include high efficiency obtained regardless of the chain length, high chemoselectivity toward terminal alkenes over internal ones, and retention of the stereoconfiguration of the stereocenter on the alkyl chain.

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Direct Alkenylation of Allylbenzenes via Chelation-Assisted C-C Bond Cleavage

Onodera S., Ishikawa S., Kochi T., Kakiuchi F.

Journal of the American Chemical Society （Journal of the American Chemical Society）  140 （ 31 ） 9788 - 9792 2018年08月

ISSN  00027863

　概要を見る

© 2018 American Chemical Society. A novel method for direct transformation of allyl groups in allylbenzene derivatives to alkenyl groups via rhodium-catalyzed C-C bond cleavage is reported. The alkenylation with styrenes of allylbenzenes containing pyridyl and pyrazolyl groups as a directing group proceeded efficiently to give alkenylation products. We also developed a new protocol for transformation of an ortho-prenylated phenol to an aniline derivative.

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Palladium-Catalyzed C−H Iodination of N-(8-Quinolinyl)benzamide Derivatives Under Electrochemical and Non-Electrochemical Conditions

Sano K., Kimura N., Kochi T., Kakiuchi F.

Asian Journal of Organic Chemistry （Asian Journal of Organic Chemistry）  7 （ 7 ） 1311 - 1314 2018年07月

ISSN  21935807

　概要を見る

© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Palladium-catalyzed ortho-selective C−H iodination of N-(8-quinolinyl)benzamides proceeded using I2 under both electrochemical and non-electrochemical conditions. The C−H iodination at 90 °C under base-free conditions provided high yields of the iodination products. The use of anodic oxidation increased the efficiency of the iodination at sterically-hindered positions.

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Iron-Catalyzed Regioselective Anti-Markovnikov Addition of C-H Bonds in Aromatic Ketones to Alkenes

Naoki Kimura, Takuya Kochi, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 139 （ 42 ） 14849 - 14852 2017年10月

研究論文（学術雑誌）, 共著, 査読有り

Synthesis of Fluorine-Containing Tetraarylanthracenes via Ruthenium-Catalyzed C-O or C-F Arylation and Their Crystal Structures

Akiko Izumoto, Hikaru Kondo, Takuya Kochi, Fumitoshi Kakiuchi

Synlett 28 （ 19 ） 2609 - 2613 2017年11月

研究論文（学術雑誌）, 共著, 査読有り

Formation of α-Monosubstituted Propargylamines from Terminal Alkynes and Secondary Amines Using a (PNO)Rh/Cu Tandem Catalyst System

Shotaro Takano, Takuya Kochi, Fumitoshi Kakiuchi

Chem. Lett. （Chemical Society of Japan）  46 （ 11 ） 1620 - 1623 2017年09月

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  1348-0715

　概要を見る

A novel (PNO)Rh/CuBr (PNO: phosphine-quinolinolate) tandem catalyst system was developed for facile synthesis of α-monosubstituted propargylamines from aliphatic terminal al-kynes and secondary amines. Various terminal alkynes and amines were applicable to this reaction and the corresponding propargylamines were obtained in good yields.

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Palladium-Catalyzed Ortho-Selective C-H Chlorination of Benzamide Derivatives under Anodic Oxidation Conditions

Miki Konishi, Kazuya Tsuchida, Katsuya Sano, Takuya Kochi, Fumitoshi Kakiuchi

J. Org. Chem. 82 （ 16 ） 8716 - 8724 2017年07月

研究論文（学術雑誌）, 共著, 査読有り

Synthesis of Dibenzo[h,rst]pentaphenes and Dibenzo[fg,qr]pentacenes by the Chemoselective C–O Arylation of Dimethoxyanthraquinones

Yusuke Suzuki, Kohei Yamada, Kentaro Watanabe, Takuya Kochi, Yutaka Ie, Yoshio Aso, Fumitoshi Kakiuchi

Org. Lett. 19 （ 14 ） 3791 - 3794 2017年07月

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-Catalyzed Ortho C–H Arylation of Aromatic Nitriles with Arylboronates and Observation of Partial Para Arylation

Yuta Koseki, Kentaroh Kitazawa, Masashi Miyake, Takuya Kochi, Fumitoshi Kakiuchi

J. Org. Chem. 82 （ 13 ） 6503 - 6510 2016年12月

研究論文（学術雑誌）, 共著, 査読有り

Selective Monoarylation of Aromatic Ketones and Esters via Cleavage of Aromatic Carbon–Heteroatom Bonds by Trialkylphosphine Ruthenium Catalysts

Hikaru Kondo, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. 19 （ 4 ） 794 - 797 2017年02月

研究論文（学術雑誌）, 共著, 査読有り

Syntheses of RuHCl(CO)(PAr3)3 and RuH2(CO)(PAr3)3 Containing Various Triarylphosphines and Their Use for Arylation of Sterically Congested Aromatic C–H Bonds

Yohei Ogiwara, Masashi Miyake, Takuya Kochi, Fumitoshi Kakiuchi

Organometallics （American Chemical Society）  36 （ 1 ） 159 - 164 2016年08月

研究論文（学術雑誌）, 査読有り,  ISSN  1520-6041

　概要を見る

A series of ruthenium complexes, RuHCl(CO)(PAr3)3 and RuH2(CO)(PAr3)3, containing various triarylphosphines were synthesized. Screening of these complexes as catalysts for direct arylation of sterically congested ortho C-H bonds of aromatic ketones improved the yields of the arylation products.

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Synthesis and reactivity of phosphine-quinolinolato rhodium complexes: Intermediacy of vinylidene and (amino)carbene complexes in the catalytic hydroamination of terminal alkynes

Shotaro Takano, Takuya Kochi, and Fumitoshi Kakiuchi

Organometallics （AMER CHEMICAL SOC）  35 （ 24 ） 4112 - 4125 2016年12月

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  0276-7333

　概要を見る

We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.

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Chain-walking cycloisomerization of 1,n-dienes catalyzed by pyridine–oxazoline palladium catalysts and its application to asymmetric synthesis

Taro Hamasaki, Fumitoshi Kakiuchi, and, Takuya Kochi

Chem. Lett. （CHEMICAL SOC JAPAN）  45 （ 3 ） 297 - 299 2016年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  0366-7022

　概要を見る

Palladium catalysts possessing pyridine oxazoline ligands were found to catalyze the chain-walking cycloisomerization of 1,n-dienes to form five-membered rings and were particularly effective for the reaction of 1,14-dienes. Asymmetric synthesis of cyclopentane derivatives was also achieved for the reaction of 1,n-dienes using chiral pyridine oxazoline ligands.

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Chain walking as a strategy for carbon–carbon bond formation at unreactive sites in organic synthesis: Catalytic cycloisomerization of various 1,n-dienes

Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, and, Takuya Kochi

J. Am. Chem. Soc. 137 （ 51 ） 16163-16171 2015年

研究論文（学術雑誌）, 共著, 査読有り

Catalytic formation of α-aryl ketones by C-H functionalization with cyclic alkenyl carbonates and one-pot synthesis of isocoumarins

Yusuke Hara, Shunsuke Onodera, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. （AMER CHEMICAL SOC）  17 （ 19 ） 4850 - 4853 2015年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  1523-7060

　概要を見る

We report here a method for direct catalytic introduction of simple alpha-acylalkyl groups via rhodium-catalyzed C-H functionalization with cyclic alkenyl carbonates, synthetic equivalents to enolates bearing leaving groups. The reaction proceeded smoothly without using bases to give a-aryl ketones in high yields. Various nitrogen-containing aromatic rings and amide groups serve as directing groups. 3-Substituted isocoumarins can also be prepared by one-pot C-H functionalization/cyclization.

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Ruthenium-catalyzed monoalkenylation of aromatic ketones via cleavage of carbon-heteroatom bonds and its unconventional chemoselectivity

Hikaru Kondo, Nana Akiba, Takuya Kochi, Fumitoshi Kakiuchi

Angew. Chem., Int. Ed. 54 （ 32 ） 9293 - 9297 2015年

研究論文（学術雑誌）, 共著, 査読有り

Palladium-catalyzed regioselective homocoupling of arenes using anodic oxidation: formal electrolysis of aromatic carbon–hydrogen bonds

Fumito Saito, Hiroko Aiso, Takuya Kochi, Fumitoshi Kakiuchi

Organometallics （AMER CHEMICAL SOC）  33 （ 22 ） 6704 - 6707 2014年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  0276-7333

　概要を見る

Palladium-catalyzed regioselective homocoupling of arylpyridines under anodic oxidation conditions was achieved in the presence of I-2. The dimerization of meta-substituted arylpyridines proceeded selectively at less-sterically congested ortho-positions, and the selectivity is different from that reported for the palladium-catalyzed dimerization using Oxone as an oxidant. The dimerization also proceeds using catalytic amounts of both Pd(OAc)(2) and I-2 under the electrochemical reaction conditions.

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Ruthenium-catalyzed ortho-selective aromatic C-H alkenylation with alkenyl carbonates

Yohei Ogiwara, Takuya Kochi, Fumitoshi Kakiuchi

Chem. Lett. 43 （ 5 ） 667-669 2014年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-catalyzed ortho-selective C-H alkenylation of aromatic compounds with alkenyl esters and ethers

Yohei Ogiwara, Masaru Tamura, Takuya Kochi, Yusuke Matsuura, Naoto Chatani, Fumitoshi Kakiuchi

Organometallics 33 （ 1 ） 402-420 2014年

研究論文（学術雑誌）, 共著, 査読有り

Copper-catalyzed electrochemical chlorination of 1,3-dicarbonyl compounds using hydrochloric acid

Kazuya Tsuchida, Takuya Kochi, and Fumitoshi Kakiuchi

Asian J. Org. Chem. （WILEY-V C H VERLAG GMBH）  2 （ 11 ） 935 - 937 2013年

研究論文（学術雑誌）, 共著, 査読有り,  ISSN  2193-5807

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Ruthenium-catalyzed reductive deamination and tandem alkylation of aniline derivatives

Tetsuro Koreeda, Takuya Kochi, Fumitoshi Kakiuchi

J. Organomet. Chem. 741-742   148-152 2013年

研究論文（学術雑誌）, 共著, 査読有り

Rhodium-catalyzed dimerization of arylacetylenes and addition of malonates to 1,3-enynes

Katsufumi Mochizuki, Kazunori Sakai, Takuya Kochi, Fumitoshi Kakiuchi

Synthesis 45 （ 15 ） 2088-2092 2013年

研究論文（学術雑誌）, 共著, 査読有り

Rhodium-catalyzed intermolecular [2 + 2] cycloaddition of terminal alkynes with electron-deficient alkenes

Kazunori Sakai, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. 15 （ 5 ） 1024-1027 2013年

研究論文（学術雑誌）, 共著, 査読有り

Substituent effects on stoichiometric and catalytic cleavage of carbon–nitrogen bonds in aniline derivatives by ruthenium–phosphine complexes

Tetsuro Koreeda, Takuya Kochi, Fumitoshi Kakiuchi

Organometallics 32 （ 2 ） 682-690 2013年

研究論文（学術雑誌）, 共著, 査読有り

Chain-walking strategy for organic synthesis: catalytic cycloisomerization of 1,n-dienes

Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 134 （ 40 ） 16544-16547 2012年

研究論文（学術雑誌）, 共著, 査読有り

Catalytic electrochemical C–H iodination and one-pot arylation by ON/OFF switching of electric current

Hiroko Aiso, Takuya Kochi, Hitoshi Mutsutani, Takamasa Tanabe, Shigeru Nishiyama, Fumitoshi Kakiuchi

J. Org. Chem. 77 （ 17 ） 7718-7724 2012年

研究論文（学術雑誌）, 共著, 査読有り

Short synthesis of alkyl-substituted acenes using carbonyl-directed C–H and C–O functionalization

Daiki Matsumura, Kentaroh Kitazawa, Seiya Terai, Takuya Kochi, Yutaka Ie, Masashi Nitani, Yoshio Aso, Fumitoshi Kakiuchi

Org. Lett. 14 （ 15 ） 3882-3885 2012年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-catalyzed arylation of fluorinated aromatic ketones via ortho-selective carbon–fluorine bond cleavage

Keisuke Kawamoto, Takuya Kochi, Mitsuo Sato, Eiichiro Mizushima, Fumitoshi Kakiuchi

Tetrahedron Lett. 52 （ 44 ） 5888-5890 2011年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-Catalyzed Acylation of Arylpyridines with Acyl Chlorides via ortho-Selective C-H Bond Cleavage

Takuya Kochi, Aoi Tazawa, Kazuki Honda, Fumitoshi Kakiuchi

Chem. Lett. 40 （ 9 ） 1018-1020 2011年

研究論文（学術雑誌）, 共著, 査読有り

Rhodium-Catalyzed anti-Markovnikov Addition of Secondary Amines to Arylacetylenes at Room Temperature

Kazunori Sakai, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. 13 （ 15 ） 3928-3931 2011年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-Catalyzed Conversion of sp3 C-O Bonds in Ethers to C-C Bonds Using Triarylboroxines

Yohei Ogiwara, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. 13 （ 12 ） 3254-3257 2011年

研究論文（学術雑誌）, 共著, 査読有り

Pd-catalyzed copolymerization of methyl acrylate with carbon monoxide: Structures, properties and mechanistic aspects toward ligand design

Akifumi Nakamura, Kagehiro Munakata, Shingo Ito, Takuya Kochi, Lung Wa Chung, Keiji Morokuma, Kyoko Nozaki

J. Am. Chem. Soc. 133 （ 17 ） 6761-6779 2011年

研究論文（学術雑誌）, 共著, 査読有り

Convenient synthesis of dibenzo[a,h]anthracenes and picenes via C–H arylation of acetophenones with arenediboronates

Kentaroh Kitazawa, Takuya Kochi, Masashi Nitani, Yutaka Ie, Yoshio Aso, Fumitoshi Kakiuchi

Chem. Lett. 40 （ 3 ） 300-302 2011年

研究論文（学術雑誌）, 共著, 査読有り

Rhodium-catalyzed anti-Markovnikov intermolecular hydroalkoxylation of terminal acetylenes

Masataka Kondo, Takuya Kochi, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 133 （ 1 ） 32-34 2011年

研究論文（学術雑誌）, 共著, 査読有り

Room-temperature regioselective C–H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates

Fumitoshi Kakiuchi, Takuya Kochi, Eiichiro Mizushima, Shinji Murai

J. Am. Chem. Soc. 132 （ 50 ） 17741-17750 2010年

研究論文（学術雑誌）, 共著, 査読有り

Control of product selectivity by styrene additive in ruthenium-catalyzed C–H arylation

Shun Hiroshima, Daiki Matsumura, Takuya Kochi, Fumitoshi Kakiuchi

Org. Lett. 12 （ 22 ） 5318-5321 2010年

研究論文（学術雑誌）, 共著, 査読有り

Why did incorporation of acrylonitrile to a linear polyethylene become possible? Comparison of phosphine‒sulfonate ligand with diphosphine and imine-phenolate ligands in the Pd-catalyzed ethylene/acrylonitrile copolymerization

Kyoko Nozaki, Shuhei Kusumoto, Shusuke Noda, Takuya Kochi, Lung Wa Chung, Keiji Morokuma

J. Am. Chem. Soc. 132 （ 45 ） 16030-16042 2010年

研究論文（学術雑誌）, 共著, 査読有り

Solution-phase assembly of a rhodium complex via specific hydrogen bonding between barbituric acid and triaminopyrimidine moieties

Masataka Kondo, Takuya Kochi, Mitsuo Sato, Aki Kitajima, Fumitoshi Kakiuchi

Chem. Lett. 39 （ 11 ） 1166-1167 2010年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-catalyzed arylation of ortho C–H bond in an aromatic ketone with an arylboronate: 8-Phenyl-1-tetralone

Kentaroh Kitazawa, Takuya Kochi, Fumitoshi Kakiuchi

Org. Synth. 87   209-217 2010年

研究論文（学術雑誌）, 共著, 査読有り

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

Kentaroh Kitazawa, Masashi Kotani, Takuya Kochi, Michael Langeloth, Fumitoshi Kakiuchi

J. Organomet. Chem. 695 （ 8 ） 1163-1167 2010年

研究論文（学術雑誌）, 共著, 査読有り

Synthesis of N-heterocyclic carbene-sulfonate palladium complexes

Yusuke Nagai, Takuya Kochi, Kyoko Nozaki

Organometallics 28 （ 20 ） 6131-6134 2009年

研究論文（学術雑誌）, 共著, 査読有り

Mechanistic studies on the formation of linear polyethylene chain catalyzed by palladium phosphine-sulfonate complexes: Experiment and theoretical studies

Shusuke Noda, Akifumi Nakamura, Takuya Kochi, Lung Wa Chung, Keiji Morokuma, Kyoko Nozaki

J. Am. Chem. Soc. 131 （ 39 ） 14088-14100 2009年

研究論文（学術雑誌）, 共著, 査読有り

Palladium-catalyzed aromatic C–H halogenation with hydrogen halides by means of electrochemical oxidation

Fumitoshi Kakiuchi, Takuya Kochi, Hitoshi Mutsutani, Noboru Kobayashi, Seiya Urano, Mitsuo Sato, Shigeru Nishiyama, Takamasa Tanabe

J. Am. Chem. Soc. 131 （ 32 ） 11310-11311 2009年

研究論文（学術雑誌）, 共著, 査読有り

Cleavage of C–N bonds in aniline derivatives on a ruthenium center and its relevance to catalytic C–C bond formation

Tetsuro Koreeda, Takuya Kochi, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 131 （ 21 ） 7238-7239 2009年

研究論文（学術雑誌）, 共著, 査読有り

Convenient synthesis of tetra- and hexaarylanthracenes by means of RuH2(CO)(PPh3)3-catalyzed C–H arylation of anthraquinone with arylboronates

Kentaroh Kitazawa, Takuya Kochi, Mitsuo Sato, Fumitoshi Kakiuchi

Org. Lett. 11 （ 9 ） 1951-1954 2009年

研究論文（学術雑誌）, 共著, 査読有り

Ruthenium-catalyzed amino- and alkoxycarbonylations with carbamoyl chlorides and alkyl chloroformates via aromatic C–H bond cleavage

Takuya Kochi, Seiya Urano, Hajime Seki, Eiichiro Mizushima, Mitsuo Sato, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 131 （ 8 ） 2792-2793 2009年

研究論文（学術雑誌）, 共著, 査読有り

Unique effect of coordination of an alkene moiety in products on ruthenium-catalyzed chemoselective C–H alkenylation

Satoshi Ueno, Takuya Kochi, Naoto Chatani, Fumitoshi Kakiuchi

Org. Lett. 11 （ 4 ） 855-858 2009年

研究論文（学術雑誌）, 共著, 査読有り

Synthesis of allylnickel complexes with phosphine sulfonate ligands and their application for olefin polymerization without activators

Shusuke Noda, Takuya Kochi, Kyoko Nozaki

Organometallics 28 （ 2 ） 656-658 2009年

研究論文（学術雑誌）, 共著, 査読有り

Regio-controlled copolymerization of methyl acrylate with carbon monoxide

Akifumi Nakamura, Kagehiro Munakata, Takuya Kochi, Kyoko Nozaki

J. Am. Chem. Soc. 130 （ 26 ） 8128-8129 2008年

研究論文（学術雑誌）, 共著, 査読有り

The Ru(cod)(cot)-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenyl Acetates

Yusuke Matsuura, Masaru Tamura, Takuya Kochi, Mitsuo Sato, Naoto Chatani, Fumitoshi Kakiuchi

J. Am. Chem. Soc. 129   9858-9859 2007年

研究論文（学術雑誌）, 共著, 査読有り

Formation of Linear Copolymers of Ethylene and Acrylonitrile Catalyzed by Phosphine Sulfonate Palladium Complexes

Takuya Kochi, Shusuke Noda, Kenji Yoshimura, Kyoko Nozaki

J. Am. Chem. Soc. 129   8948-8949 2007年

研究論文（学術雑誌）, 共著, 査読有り

Alternating Copolymerization of Vinyl Acetate with Carbon Monoxide

Takuya Kochi, Akifumi Nakamura, Hirotsugu Ida, Kyoko Nozaki

J. Am. Chem. Soc. 129   7770-7771 2007年

研究論文（学術雑誌）, 共著, 査読有り

Synthesis of anionic methylpalladium complexes with phosphine-sulfonate ligands and their activities for olefin polymerization

Takuya Kochi, Kenji Yoshimura, Kyoko Nozaki

Dalton Trans.    25-27 2006年

研究論文（学術雑誌）, 共著, 査読有り

Asymmetric α-Alkylation of N'-tert-Butanesulfinyl Amidines. Application to the Total Synthesis of (6R,7S)-7-Amino-7,8-dihydro-α-bisabolene

Takuya Kochi, d Jonathan A. Ellman

J. Am. Chem. Soc. 126   15652-15653 2004年

研究論文（学術雑誌）, 共著, 査読有り

Development and application of a new general method for the asymmetric synthesis of syn- and anti-1,3-amino alcohols

Takuya Kochi, Tony P. Tang, Jonathan A. Ellman

J. Am. Chem. Soc. 125   11276-11282 2003年

研究論文（学術雑誌）, 共著, 査読有り

Stepwise construction of a Re-Pd heterodinuclear core inside the cavity of p-tBu-calix[4]arene

Kentarou Iwasa, Takuya Kochi, Youichi Ishii

Angew. Chem. Int. Ed. 42   3658-3660 2003年

研究論文（学術雑誌）, 共著, 査読有り

Asymmetric synthesis of syn- and anti-1,3-amino alcohols

Takuya Kochi, Tony P. Tang, Jonathan A. Ellman

J. Am. Chem. Soc. 124   6518-6519 2002年

研究論文（学術雑誌）, 共著, 査読有り

Synthesis and structures of heterobimetallic Ir2M (M=Pd, Pt) sulfido clusters and their catalytic activity for regioselective addition of alcohols to internal 1-aryl-1-alkynes

Dai Masui, Takuya Kochi, Zhen Tang, Youichi Ishii, Yasushi Mizobe, Masanobu Hidai

J. Organomet. Chem. 620   69-79 2001年

研究論文（学術雑誌）, 共著, 査読有り

Rh4S7 and Ir3CuS6 clusters with di- and trisulfido ligands derived from dinuclear hydrogensulfido complexes

Takuya Kochi, Yoshiaki Tanabe, Zhen Tang, Youichi Ishii, Masanobu Hidai

Chem. Lett.    1279-1280 1999年

研究論文（学術雑誌）, 共著, 査読有り

Synthesis and reactivities of Ir2Ru heterobimetallic sulfido clusters derived from a hydrogensulfido-bridged diiridium complex

Takuya Kochi, Yasuo Nomura, Zhen Tang, Youichi Ishii, Yasushi Mizobe, Masanobu Hidai

J. Chem. Soc., Dalton. Trans.    2575-2582 1999年

研究論文（学術雑誌）, 共著, 査読有り