Researcher Database

Yasunori Yamamoto
Creative Research Institution Institute for Chemical Reaction Design and Discovery
Specially Appointed Associate Professor

Researcher Profile and Settings

Affiliation

  • Creative Research Institution Institute for Chemical Reaction Design and Discovery

Job Title

  • Specially Appointed Associate Professor

Research funding number

  • 30271646

J-Global ID

Research Interests

  • イリジウム触媒   ロジウム触媒   アリルホウ素化合物   クロスカップリング反応   アリル型ホウ素化合物   異性化反応   ニッケル触媒   触媒的ヒドロホウ素化   白金触媒   触媒的異性化反応   カップリング反応   ホモアリルアルコール   1,4-付加反応   ドミノアリル化反応   アリルホウ素化反応   触媒的ヒドロホウ素化反応   アリルシリルエーテル   イリジウム錯体   クロスメタセシス   ルイス酸触媒   アルケニルホウ素化合物   分子内アリルシリル化   ロジウム錯体   シリルエノールエーテル   分子内付加反応   末端アルキン二量体反応   触媒的二重結合異性化反応   ハロボレーション   γ-ボリルアリルシラン   シス選択的ヒドロホウ素化反応   有機ホウ素化学   有機金属化学   有機合成化学   Synthetic Organic Chemistry Organometallic Chemistry Organoboron Chemistry   

Research Areas

  • Nanotechnology/Materials / Synthetic organic chemistry
  • Life sciences / Bioorganic chemistry
  • Nanotechnology/Materials / Structural/physical organic chemistry

Academic & Professional Experience

  • 2020/04 - Today Institute for Chemical Reaction Design and Discovery
  • 2018/12 - 2020/03 Faculty of Engineering, Hokkaido University
  • 2012/04 - 2018/11 Hokkaido University Faculty of Engineering
  • 2010/04 - 2012/03 Hokkaido University Faculty of Engineering
  • 2007/04 - 2010/03 Hokkaido University Graduate School of Engineering
  • 1995/04 - 2007/03 Hokkaido University Graduate School of Engineering
  • 1993/04 - 1995/03 三菱化学株式会社 研究員

Association Memberships

  • 有機合成化学協会東北・北海道支部   有機合成化学協会 東北・北海道支部 庶務幹事   日本化学会北海道支部   日本化学会・有機合成化学協会・米国化学会   日本化学会 北海道支部   日本化学会   Japan American Chemical Society   The Chemical Society of Japan The Society of Synthetic Organic Chemistry   

Research Activities

Published Papers

  • Tomohiko Shirai, Tomoya Iwasaki, Kazuya Kanemoto, Yasunori Yamamoto
    Chemistry – An Asian Journal 15 (12) 1858 - 1862 1861-4728 2020/05/27 [Refereed][Not invited]
  • Tomohiko Shirai, Kazuki Sugimoto, Masaya Iwasaki, Ryuki Sumida, Harunori Fujita, Yasunori Yamamoto
    Synlett 30 (8) 972 - 976 2019/04 [Refereed][Not invited]
  • Tomohiko Shirai, Takakazu Okamoto, Yasunori Yamamoto
    Asian Journal of Organic Chemistry 7 (6) 1054 - 1056 2193-5807 2018/06/01 [Refereed][Not invited]
     
    An efficient and highly enantioselective direct alkylation process of acetanilides with 2-norbornene using a bis(phosphoramidite) cationic Ir catalytic system (up to 99 % ee) has been reported. This methodology allows the facile preparation of enantiomerically enriched exo-2-(bicyclo[2.2.1]heptan-2-yl)anilines, which can be readily transformed into other functionalities.
  • Tomohiko Shirai, Yasunori Yamamoto
    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry 76 (6) 604 - 614 0037-9980 2018 [Refereed][Not invited]
     
    In this article, we have summarized our recent efforts to use chiral bidentate phosphoramidites for asymmetric hydroarylation. Asymmetric intramolecular hydroarylation of a-ketoamides gave various types of optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities (84-98% ee). This asymmetric hydroarylation was realized by the use of the cationic iridium complex [Ir(cod)2] (BArF4) and the chiral O-linked bidentate phosphoramidite (RR)-Me-BIPAM. A catalytic cycle involving C-H bond cleavage to give an Ar-[Ir]+ intermediate, insertion of a carbonyl group into the aryl-iridium bond, giving iridium alkoxide, and finally reductive elimination to reproduce active [Ir] + species was proposed. The mechanistic insight for the iridium hydride species indicated that the C-H bond cleavage is caused in a reversible manner. Because the kinetic isotope effect was determined that kH/kD was 1.85, the C-H bond cleavage step was not included in the turnover-limiting step. In addition, Hammett studies of substrates (p=-0.99) demonstrated that electron-donating groups at the para position to the reactive C-H bond accelerate the reaction rate. This linear relationship obtained in the Hammett plot indicated that the nucleophilicity of the aryl-iridium intermediate is an important factor in this reaction. All of the data indicated that carbonyl insertion into aryliridium was included in the turnover-limiting step of the catalytic cycle. Meanwhile, highly enantioselective cationic iridium-catalyzed hydroarylation of bicycloalkenes, by carbonyl-directed C-H bond cleavage, was accomplished using a newly synthesized sulfur-linked bis (phosphoramidite) ligand (S-Me-BIPAM). The reaction provided alkylated acetophenone or benzamide derivatives in moderate to excellent yields and good to excellent enantioselectivities. Notably, the hydroarylation reaction of 2-norbornene with AA-dialkylbenzamide proceeded with excellent enantioselectivity (up to 99% ee) and high selectivity for the mono-ortho-alkylation product. Deuterium incorporation experiments indicated that C-H bond cleavage occurs in a non-reversible manner prior to the alkene insertion. A kinetic isotope effect (KIE) of 2.08 indicated that the turnover - limiting step included the C-H bond cleavage step.
  • Jumpei Taguchi, Toshiki Ikeda, Rina Takahashi, Ikuo Sasaki, Yasushi Ogasawara, Tohru Dairi, Naoya Kato, Yasunori Yamamoto, Jeffrey W. Bode, Hajime Ito
    Angewandte Chemie Wiley-Blackwell 129 (44) 14035  2017/10 [Refereed][Not invited]
  • Jumpei Taguchi, Toshiki Ikeda, Rina Takahashi, Ikuo Sasaki, Yasushi Ogasawara, Tohru Dairi, Naoya Kato, Yasunori Yamamoto, Jeffrey W. Bode, Hajime Ito
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 56 (44) 13847 - 13851 1433-7851 2017/10 [Refereed][Not invited]
     
    A concise synthesis of acylborons was achieved by ozonolysis of alkenyl MIDA (N-methyliminodiacetic acid) boronates. This reaction exhibits excellent functional-group tolerance and is applicable to various acyl MIDA boronates and potassium acyltrifluroborates (KATs) which could not be synthesized by previous methods. In addition, alpha-amino acylborons, which would be essential for peptide ligations, were prepared for the first time. The acylboron of l-alanine was obtained in high enantiopurity and found to be configurationally stable. Oligopeptide synthesis between the alpha-amino KATs and amino acid in dilute aqueous media was studied.
  • Yoshio Hato, Yoshihiro Oonishi, Yasunori Yamamoto, Kiyohiko Nakajima, Yoshihiro Sato
    JOURNAL OF ORGANIC CHEMISTRY 81 (17) 7847 - 7854 0022-3263 2016/09 [Refereed][Not invited]
     
    Stereoselective construction of spiro-fused tricyclic compounds from enynes having a tethered imine with diazoalkenes was achieved by Rh(I)- and Rh(II)-catalyzed sequential reactions. This method consists of three reactions, Rh(I)-catalyzed cyclization of enynes with a tethered imine, Rh(II)-catalyzed cyclopropanation with diazoalkenes, and Cope rearrangement. Notably, the sequential reactions can be operated in one pot, in which Rh(I) and Rh(II) catalysts work in relay without any serious catalyst deactivation to afford the spirocycles in a stereoselective manner.
  • Naoya Kato, Tomohiko Shirai, Yasunori Yamamoto
    CHEMISTRY-A EUROPEAN JOURNAL 22 (23) 7739 - 7742 0947-6539 2016/06 [Refereed][Not invited]
     
    Chiral rhodium(I)-catalyzed highly enantioselective arylation of aliphatic N-sulfonyl aldimines with arylboronic acids has been developed. This transformation is achieved by the use of a rhodium/bis(phosphoramidite) catalyst to give enantiomerically enriched a-branched amines (up to 99% ee). In addition, this system enables efficient synthesis of (+)-NPS R-568 and Cinacalcet which are calcimimetic agents.
  • Naoya Kato, Tomohiko Shirai, Yasunori Yamamoto
    Chemistry - A European Journal 22 (23) 7739 - 7742 1521-3765 2016 [Refereed][Not invited]
     
    Chiral rhodium(I)-catalyzed highly enantioselective arylation of aliphatic N-sulfonyl aldimines with arylboronic acids has been developed. This transformation is achieved by the use of a rhodium/bis(phosphoramidite) catalyst to give enantiomerically enriched α-branched amines (up to 99 % ee). In addition, this system enables efficient synthesis of (+)-NPS R-568 and Cinacalcet which are calcimimetic agents.
  • Masaaki Yohda, Yasunori Yamamoto
    TETRAHEDRON-ASYMMETRY 26 (24) 1430 - 1435 0957-4166 2015/12 [Refereed][Not invited]
     
    We have developed an enantioselective synthesis of 3-aryl-3-hydroxybenzofuran-2-ones via the ruthenium-catalyzed 1,2-addition of arylboronic acids to benzofuran-2,3-diones. The use of RuCl2(PPh3)(3) with a chiral bidentate phosphoramidite ligand [(R,R)-Me-BIPAM] in the presence of a small amount of acetonitrile (20 mol %) gave optically active 3-aryl-3-hydroxybenzofuran-2-ones with up to 96% ee. This reaction is the first example of a catalytic asymmetric 1,2-addition reaction of arylboronic acids to benzofuran-2,3-diones for the highly efficient and enantioselective synthesis of quaternary carbon containing benzofuran-2-ones. (c) 2015 Elsevier Ltd. All rights reserved.
  • Tomohiko Shirai, Yasunori Yamamoto
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54 (34) 9894 - 9897 1433-7851 2015/08 [Refereed][Not invited]
     
    Highly enantioselective cationic iridium-catalyzed hydroarylation of bicycloalkenes, by carbonyl-directed C-H bond cleavage, was accomplished using a newly synthesized sulfur-linked bis(phosphoramidite) ligand (S-Me-BIPAM). The reaction provides alkylated acetophenone or benzamide derivatives in moderate to excellent yields and good to excellent enantioselectivities. Notably, the hydroarylation reaction of 2-norbornene with N,N-dialkylbenzamide proceeds with excellent enantioselectivity (up to 99% ee) and high selectivity for the mono-ortho-alkylation product.
  • Tomohiko Shirai, Yasunori Yamamoto
    ORGANOMETALLICS 34 (14) 3459 - 3463 0276-7333 2015/07 [Refereed][Not invited]
     
    Results of mechanistic studies on asymmetric hydroarylation of alpha-keto amides Via direct C-H bond addition to a carbonyl group catalyzed by a cationic Ir/Me-BIPAM complex are presented in this paper. A catalytic cycle involving C-H bond cleavage to give an Ar-[Ir](+) intermediate, insertion of a carbonyl group into the aryl-iridium bond, giving iridium alkoxide, and finally reductive elimination to reproduce active [Ir](+) species is proposed. The mechanistic insight for the iridium hydride species indicated that the C-H bond cleavage is caused in a reversible manner. Furthermore, the kinetic isotope effect was measured by product analysis of the reaction to compare HID, and it was determined that k(H)/k(D) was 1.85. These experimental results suggest that the C-H bond cleavage step is not included hi the turnover-limiting step. In addition, Hammett studies of substrates (rho = -0.99) demonstrated that electron-donating groups at the para position to the reactive C-H bond accelerate the reaction rate. This linear relationship obtained in the Hammett plot indicates that the nucleophilicity of the aryl-iridium intermediate is an important factor in this reaction. All of the data indicate that carbonyl insertion into aryl-iridium is included in the turnover-limiting step of the catalytic cycle.
  • Masaaki Yohda, Yasunori Yamamoto
    ORGANIC & BIOMOLECULAR CHEMISTRY 13 (44) 10874 - 10880 1477-0520 2015 [Refereed][Not invited]
     
    Ruthenium/Me-BIPAM-catalyzed asymmetric addition of arylboronic acids to methyl 2-formylbenzoates afforded chiral 3-aryl-isobenzofuranones. [RuCl2(p-cymene)](2)/Me-BIPAM and RuCl2(PPh3)(3)/Me-BIPAM catalyst systems tolerate a variety of functional groups and give high yields with high enantioselectivities.
  • Tomohiko Shirai, Hajime Ito, Yasunori Yamamoto
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 (10) 2658 - 2661 1433-7851 2014/03 [Refereed][Not invited]
     
    Asymmetric intramolecular direct hydroarylation of -ketoamides gives various types of optically active 3-substituted 3-hydroxy-2-oxindoles in high yields with complete regioselectivity and high enantioselectivities (84-98% ee). This is realized by the use of the cationic iridium complex [Ir(cod)(2)](BAr4F) and the chiral O-linked bidentate phosphoramidite (R,R)-Me-BIPAM.
  • Shohei Sakashita, Miho Takizawa, Juugaku Sugai, Hajime Ito, Yasunori Yamamoto
    ORGANIC LETTERS 15 (17) 4308 - 4311 1523-7060 2013/09 [Refereed][Not invited]
     
    Palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of tetrabutylammonium 2-pyridyltriolborate salts with various aryl (heteroaryl) chlorides can produce the corresponding desired coupling products with good to excellent yields. These tetrabutylammonium salts are more reactive than the corresponding lithium salts. The coupling reactions with aryl chlorides progressed in the presence of PdCl(2)dcpp (3 mol %) and Cul/MeNHCH2CH2OH (20 mol %) in anhydrous DMF without bases.
  • Yasunori Yamamoto
    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry 71 (7) 716 - 727 0037-9980 2013 [Refereed][Not invited]
     
    The transition metal catalyzed addition reactions of organic electrophiles to activated alkenes, imines and carbonyl compounds are powerful tools for new carbon-carbon bonds with high enantio-selectivity. Chiral bidentate phosphoramidite ligands (Me-BIPAM and N-Me-BIPAM) were synthesized from linked-BINOL as new ligands for asymmetric addition reactions of arylboronic acids. These bidentate phosphoramidite ligands appear to be highly effective for rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to α,β-unsaturated ketones. In the course of our study on bidentate phosphoramidites as a chiral ligand for enantioselective bond-forming reactions, we found that N-Me-BIPAM is effective for arylation of N-sulfonyl arylimines with arylboronic acids. Me-BIPAM was found to be highly efficient for ruthenium-catalyzed enantioselective arylation of aldehydes, α-ketoesters, glyoxylate, and isatins. In this review, we focus on chiral bidentate phosphoramidite ligands (Me-BIPAM and N-Me-BIPAM) for asymmetric carbon-carbon bond-forming reactions of arylboronic acids.
  • Yasunori Yamamoto, Kazunori Kurihara, Yoshinori Takahashi, Norio Miyaura
    MOLECULES 18 (1) 14 - 26 1420-3049 2013/01 [Refereed][Invited]
     
    A new bidentate phosphoramidite (N-Me-BIPAM) based on Shibasaki's N-linked BINOL was synthesized. This ligand appears to be highly effective for rhodium-catalyzed asymmetric conjugated addition of arylboronic acids to alpha,beta-unsaturated enones. The reaction of ortho-substituted arylboronic acid with acyclic and cyclic enones provides the corresponding products in good yields and enantioselectivities.
  • Yasunori Yamamoto, Kazuya Ikizakura, Hajime Ito, Norio Miyaura
    MOLECULES 18 (1) 430 - 439 1420-3049 2013/01 [Refereed][Invited]
     
    We newly developed lithium methyltriolborate as an air-stable white solid that is convenient to handle. The good performance of this triolborate for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions with haloarenes. Cross-coupling reaction of [MeB(OCH2)(3)CCH3]Li with aryl halides occurred in the presence of Pd(OAc)(2)/RuPhos complex in refluxing MeOH/H2O and the absence of bases.
  • Yasunori Yamamoto, Masaaki Yohda, Tomohiko Shirai, Hajime Ito, Norio Miyaura
    CHEMISTRY-AN ASIAN JOURNAL 7 (10) 2446 - 2449 1861-4728 2012/10 [Refereed][Not invited]
     
    A chiral O-linked C2-symmetric bidentate phosphoramidite (Me-BIPAM) was found to be efficient for the ruthenium-catalyzed addition of arylboronic acids to isatins. Asymmetric synthesis of 3-aryl-3-hydroxy-2-oxindoles by 1,2-addition of arylboronic acids to isatins was carried out in the presence of [RuCl2(PPh3)3]/(R,R)-Me-BIPAM and KF, resulting in an enantioselectivity as high as 90?% ee. It was found that the reaction with N-protected isatins proceeds with high yields and good enantioselectivities. The best protective groups on the nitrogen atom were different depending on the substituents on the aromatic ring. The use of a N-benzyl group resulted in excellent enantioselectivities in many substrates compared with other groups.
  • Yasunori Yamamoto
    HETEROCYCLES 85 (4) 799 - 819 0385-5414 2012/04 [Refereed][Invited]
     
    This review summarizes metal-catalyzed C-C and C-N bond-forming reactions using novel heteroaryltriolborate salts for palladium- or copper-catalyzed cross-coupling reactions with arylhalides or amines and for rhodium-catalyzed addition reactions to alpha,beta-unsaturated carbonyl compounds or imines.
  • Yasunori Yamamoto, Tomohiko Shirai, Norio Miyaura
    CHEMICAL COMMUNICATIONS 48 (22) 2803 - 2805 1359-7345 2012 [Refereed][Not invited]
     
    The enantioselective synthesis of a-hydroxy esters by ruthenium-catalyzed 1,2-addition of arylboronic acids to tert-butyl glyoxylate is described. The use of RuCl2(PPh3)(3) with (R, R)-Me-BIPAM gave optically active mandelic acids of up to 99% ee. Addition of a fluoride salt such as potassium fluoride (KF) or caesium fluoride (CsF) was effective for achieving high enantioselectivities.
  • Kenya Kobayashi, Yasunori Yamamoto, Norio Miyaura
    ORGANOMETALLICS 30 (22) 6323 - 6327 0276-7333 2011/11 [Refereed][Not invited]
     
    Palladium/(4-MeO-3,5-MePh)(2)PF-Pcy(2)) catalyzed the enantioselective arylation of silyl ketene acetals with iodoarenes in the presence of TlOAc to promote transmetalation of silyl ketene acetals. The highest enantioselectivities giving alpha-arylesters up to 91% ee were achieved when (E)-1-methoxy-1-(trimethylsiloxy)propene (E/Z = 88/12) was used for the silyl ketene acetal. The effect on enantioselection of a chiral ligand is discussed on the basis of the X-ray structure of the palladium/(4-MeO-3,5-MePh)(2)PF-Pcy(2)) complex and results of DFT computational studies on mechanistic aspects of the catalytic cycle.
  • Gao-Qiang Li, Yasunori Yamamoto, Norio Miyaura
    TETRAHEDRON 67 (36) 6804 - 6811 0040-4020 2011/09 [Refereed][Not invited]
     
    A new method for simple and practical synthesis of diaryl-substituted arenes using potassium aryltriolborates was developed. Double-cross-coupling of dibromo arenes with aryltriolborates was carried out in the presence of a palladium catalyst, such as Pd(OAc)(2), Pd(PPh3)(4) or Pd(OAc)(2)/BIPHEP. The use of CuCl (40 mol %) with a palladium catalyst was found to be highly effective to give diaryl-substituted aromatic compounds in good yields. (C) 2011 Elsevier Ltd. All rights reserved.
  • Akira Suzuki, Yasunori Yamamoto
    CHEMISTRY LETTERS 40 (9) 894 - 901 0366-7022 2011/09 [Refereed][Not invited]
     
    The palladium-catalyzed cross-coupling reaction between different types of organoboron compounds and various organic halides or triflates in the presence of base provides a powerful and general methodology for the formation of carbon-carbon bonds. The Csp(2)-B compounds (such as aryl- and 1-alkenylboron derivatives) and Csp(3)-B compounds (alkylboron compounds) readily cross-couple with organic electrophiles to give coupled products selectively in high yields. Recently, the Csp-B compounds (1-alkynylboron derivatives) have been also observed to react with organic electrophiles to produce expected cross-coupled products. The overview of some of such coupling reactions is discussed here in this article.
  • Gao-Qiang Li, Yasunori Yamamoto, Norio Miyaura
    SYNLETT 2011 (12) 1769 - 1773 0936-5214 2011/07 [Refereed][Not invited]
     
    Tetra-ortho-substituted biaryls were synthesized by cross-coupling between 2,6-disubstituted bromoarenes and aryltriolborates possessing substituents at ortho carbon. The use of a copper(I) halide such as CuCl (20 mol%) with a palladium catalyst was found to be highly effective to give such sterically hindered biaryls in good yields.
  • Gao-Qiang Li, Shunsuke Kiyomura, Yasunori Yamamoto, Norio Miyaura
    CHEMISTRY LETTERS 40 (7) 702 - 704 0366-7022 2011/07 [Refereed][Not invited]
     
    Conversion of pinacol arylboronic esters 3 to aryl triolborates 5 via transesterification with 1,1,1-tris(hydroxymethyl)ethane (4) was established with the advantages of tolerance to various functional groups. Transesterification was carried out at 30-60 degrees C in dioxane in the presence of MOH (M = Na and K) and H2O. High yields were achieved for stable aryl triolborates 5.
  • Yasunori Yamamoto, Juugaku Sugai, Miho Takizawa, Norio Miyaura
    Organic Syntheses 88 79 - 86 1600-0730 2011/07/01 [Refereed][Not invited]
  • Yasunori Yamamoto, Tomohiko Shirai, Momoko Watanabe, Kazunori Kurihara, Norio Miyaura
    MOLECULES 16 (6) 5020 - 5034 1420-3049 2011/06 [Refereed][Not invited]
     
    A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and alpha-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and alpha-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities.
  • Xiao-Qiang Yu, Tomohiko Shirai, Yasunori Yamamoto, Norio Miyaura
    CHEMISTRY-AN ASIAN JOURNAL 6 (3) 932 - 937 1861-4728 2011/03 [Refereed][Not invited]
     
    Rhodium-catalyzed 1,4-addition of lithium 5-methyl-2-furyltriolborate ([ArBACHTUNGTRENUNG(OCH2)(3)CCH3] Li, Ar = 5-methyl-2-furyl) to unsaturated ketones to give beta-furyl ketones was followed by ozonolysis of the furyl ring for enantioselective synthesis of gamma-oxo-carboxylic acids. [RhACHTUNGTRENUNG(nbd)(2)]BF4 (nbd = 2,5-norbornadiene) chelated with 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap) or 2,3-bis(diphenylphosphino) butane (chiraphos) gave high yields and high selectivities in a range of 91-99% ee at 30 degrees C in a basic dioxane/water solution. The corresponding reaction of unsaturated esters, such as methyl crotonate, had strong resistance under analogous conditions, but the 1,4-adduct was obtained in 70% yield and with 94% ee when more electron-deficient phenyl crotonate was used as the substrate.
  • Yasunori Yamamoto, Yoshinori Takahashi, Kazunori Kurihara, Norio Miyaura
    AUSTRALIAN JOURNAL OF CHEMISTRY 64 (11) 1447 - 1453 0004-9425 2011 [Refereed][Not invited]
     
    Rhodium-catalyzed enantioselective 1,2-additions of arylboronic acids to N-tosyl furanylimine and lithium 5-methyl-2-furanyltriolborate to N-tosyl arylimines giving aryl(2-furanyl)methanamines were developed for enantioselective synthesis of arylglycines by ozonolysis of the furyl ring. A chiral N-linked C-2-symmetric bidentate phosphoramidite (N-Me-BIPAM) achieved high enantioselectivities up to 99% ee. For the direct synthesis of arylglycines, the asymmetric addition of arylboronic acids to ethyl N-p-methoxyphenyl iminoester was carried out at 80 degrees C in dioxane in the presence of Rh(acac)(C2H4)(2)/(R,R)-N-Me-BIPAM. The reaction gave optically active arylglycines in up to 99% ee.
  • Yasunori Yamamoto, Miho Takizawa, Xiao-Qiang Yu, Norio Miyaura
    HETEROCYCLES 80 (1) 359 - 368 0385-5414 2010/01 [Refereed][Invited]
     
    Cyclic triolborates possessing a heteroaromatic ring on the boron atom [ArB(OCH2)(3)CHCH3]M (M=K, Na, Li) were prepared in high yields from heteroarylboronic acids, 1,1,1-tris(hydroxymethyl)ethane (triol) and KOH or NaH. The corresponding lithium salts were synthesized from aryllithiums, B(OMe)(3) and triol. They were air-stable white solids that were convenient for handling in air. High performance of these triolborates for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions with haloarenes. Although the use of heteroarylboronic acids often results in very low yields due to competitive hydrolytic B-C bond cleavage with water under typical conditions using aqueous bases, triolborates possessing a 2-pyridyl, 3-pyridyl or 2-thiophenyl ring afforded biaryls in high yields at 50-120 degrees C in anhydrous DMF. There was a strong accelerating effect of CuI for reactions of 2- and 3-pyridylborate derivatives, whereas 2-thiophenyl derivatives reacted smoothly resulting in high yields in the absence of CuI.
  • Kazunori Kurihara, Yasunori Yamamoto, Norio Miyaura
    TETRAHEDRON LETTERS 50 (26) 3158 - 3160 0040-4039 2009/07 [Refereed][Not invited]
     
    High performance of Me-BIPAM for enantioselective hydrogenation of alpha-dehydroamino esters, enamides, and dimethyl itaconate was demonstrated. [Rh(Me-BIPAM)(diene)]X (diene = cod, nbd; X = BF(4), PF(6), SbF(6)) gave optically active beta-aryl alpha-amino esters up to 99% ee, 1-arylethylamines up to 97% ee, methyl 2-acetylaminobutanoate with 90% ee, and dimethyl 2-methylsuccinate with 97% ee under 0.3-0.8 MPa dihydrogen with 0.1-1 mol% catalyst loading. (C) 2009 Elsevier Ltd. All rights reserved.
  • Yuting Wang, Yasunori Yamamoto, Hajime Kiyono, Shiro Shimada
    JOURNAL OF THE AMERICAN CERAMIC SOCIETY 92 (4) 787 - 792 0002-7820 2009/04 [Refereed][Not invited]
     
    Synthesis of boron nitride spheres (BNS) was achieved by vapor phase pyrolysis of ammonia borane (BH(3)NH(3)) using two independently temperature-controlled furnaces in a glove box filled with N(2). The BNS were heated at 1300 degrees-1700 degrees C in flowing NH(3), N(2), or Ar by multistep heat treatment. The sizes of the BNS could be controlled by heating BH(3)NH(3) at different rates (1 degrees C/min: 300-800 nm, 5 degrees C/min: 300 nm-1.2 mu m and 10 degrees C/min: 300 nm-1.8 mu m). The microstructures of BNS heated in different ambient gases were observed using transmission electron microscopy with selected area electron diffraction. NH(3) gas produced BNS with well-crystallized surface shells and amorphous cores whereas N(2) and Ar gases crystallized the entire BNS. It is evident that of these three ambient gases (NH(3), N(2), and Ar), N(2) gas significantly enhances the crystallization of BN with randomly oriented grains.
  • Xiao-Qiang Yu, Yasunori Yamamoto, Norio Miyaura
    SYNLETT (6) 994 - 998 0936-5214 2009/04 [Refereed][Not invited]
     
    Rhodium-catalyzed asymmetric 1,4-additions of electron-deficient heteroaryl groups to alpha,beta-unsaturated carbonyl compounds were established. The reaction resulted in very low yields due to competitive C-B bond cleavage when arylboronic acids. their pinacol esters, or potassium trifluoroborates were used. However, the corresponding lithium heteroaryl(triol)borates afforded 1,4-adducts With high enantioselectivities up to 97% in the presence of a rhodium(I) catalyst chelated with a chiral BINAP or BIPAM ligand.
  • Yasunori Yamamoto, Shingo Takada, Norio Miyaura, Tetsuji Iyama, Hiroto Tachikawa
    ORGANOMETALLICS 28 (1) 152 - 160 0276-7333 2009/01 [Refereed][Not invited]
     
    Cross-coupling between bromoarenes and [(E)-CH3CH=CHCH2BF3]K (2a) by a catalyst prepared from Pd(OAc)(2) and D-t-BPF selectively provided gamma-coupling products via S(E)2' substitution. Mechanistic study of transmetalation revealed a heretofore unknown process, namely, formation of a highly electrophilic [Pd(Ar)(D-t-BPF)](+) before transmetalation with 2a. Thus, kinetic data in coupling of 4-substituted bromoarenes with 2a showed a linear positive correlation (rho = -1.1) accelerated by donating substituents. This rate-determining role of transmetalation was further confirmed by kinetic data between oxidative adducts [Pd(Ar)(Br)(D-t-BPF)] and 2a that exhibited an analogous correlation with a negative rho-value (-0.50). Theoretical study by density functional theory (DFT) calculation showed that transmetalation between [Ar-Pd](+) and 2a via an S(E)2' (open) transition state is a slightly lower energy process than an S(E)2' (closed) process. Allylic substitutions with chiral catalysts are the current topics for enantioselective C-C bond fort-nation, but the catalysts that are effective for allylic nucleophiles have remained unexplored. Among the ligands screened, (R,S)-CyPF-t-Bu was found to achieve 77-90% ee for representative para-and meta-substituted bromoarenes and 2-bromo-l-alkenes in refluxing aqueous tetrahydrofuran (THF) or MeOH. To obtain mechanistic information on enantioselection, the mode of substrate coordination to a cationic phenylpalladium intermediate was calculated, that is, the reaction stage directly preceding the stereodetermining insertion step by DFT calculation. A stable adduct between [Pd(CyPF-t-Bu)(Ph)](+) and 2a located at the C-C double bond from its re-face yielding the experimentally observed R-product is preferred thermodynamically rather than the corresponding si-coordination.
  • Kazunori Kurihara, Yasunori Yamamoto, Norio Miyauraa
    ADVANCED SYNTHESIS & CATALYSIS 351 (1-2) 260 - 270 1615-4150 2009/01 [Refereed][Not invited]
     
    A chiral N-linked C(2)-symmetric bidentate phosphoramidite (N-Me-BIPAM) was newly developed for the rhodium-catalyzed enantioselective addition of arylboronic acids to N-sulfonylimines. This ligand achieved high enantioselectivities in a range of 84-99% ee in additions of arylboronic acids to N-tosyl- and N-nosylarylaldimines.
  • Yasunori Yamamoto, Kazunori Kurihara, Norio Miyaura
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 48 (24) 4414 - 4416 1433-7851 2009 [Refereed][Not invited]
  • Takashi Nishikata, Shunsuke Kiyomura, Yasunori Yamamoto, Norio Miyaura
    SYNLETT (16) 2487 - 2490 0936-5214 2008/10 [Refereed][Not invited]
     
    An asymmetric 1,4-addition of arylboronic acids to RCH=CHCO(2)Ar (Ar = Ph or 4-acetylphenyl) was carried out at 50 degrees C in aqueous acetone in the presence of [Pd(chiraphos)(PhCN)(2)](SbF(6))(2). The reaction gave optically active P-aryl esters in Lip to 98% ee. The protocol provided a simple access to an endothelin receptor antagonist reported by SmithKline Beecham.
  • Kenya Kobayashi, Takashi Nishikata, Yasunori Yamamoto, Norio Miyaura
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 81 (8) 1019 - 1025 0009-2673 2008/08 [Refereed][Not invited]
     
    Baeyer-Villiger oxidation of chiral beta-diaryl ketones synthesized by 1,4-addition of arylboronic acids to beta-aryl-alpha,beta-unsaturated ketones catalyzed by a palladium(2+)-chiraphos complex provided optically active beta-diaryl esters up to 98% ee. The protocol was applied to the synthesis of a potent competitive muscarinic receptor antagonist, (R)-tolterodine (21), which has a chiral center consisting of two aryl rings.
  • Takao Kikuchi, Yusuke Nobuta, Junko Umeda, Yasunori Yamamoto, Tatsuo Ishiyama, Norio Miyaura
    TETRAHEDRON 64 (22) 4967 - 4971 0040-4020 2008/05 [Refereed][Not invited]
     
    A method for practical preparation of pinacolborane from borane-diethylaniline and pinacol was newly developed. Aromatic C-H borylation of arenes with pinacolborane or bis(pinacolato)diboron catalyzed by 1/2[Ir(OMe)(COD)](2)-(4,4'-di-tert-butyl-2,2'-bipyridine) at 25 degrees C in hexane to give arylboronic esters was directly followed by cross-coupling with aromatic bromides at 60 degrees C in the presence of PdCl(2)(dppf) (3.0 mol %) and K(3)PO(4) in DMF. This one-pot, two-step procedure provided a variety of unsymmetrical biaryls in high yields. (C) 2008 Elsevier Ltd. All rights reserved.
  • Yasunori Yamamoto, Takashi Nishikata, Norio Miyaura
    PURE AND APPLIED CHEMISTRY 80 (5) 807 - 817 0033-4545 2008/05 [Refereed][Not invited]
     
    An enantioselective synthesis of cyclic and acyclic P-aryl ketone and aldehydes via Pd(II)-catalyzed 1,4-addition of Ar-m [m = B(OH)(2), BF3K, Si(OMe)(3), SiF3, BiAr2] to a,p-unsaturated ketones or aldehydes is described. The catalytic cycle-involves transmetallation between Ar-m and Pd complexes as a key process, the mechanism of which is discussed on the basis of characterization of the transmetallation intermediate and electronic effect of the substituents. The enantioselection mechanism and efficiency of a chiraphos ligand for structurally planar alpha,beta-unsaturated ketones are discussed on the basis of the X-ray structure of the catalyst and results of density functional theory (DFT) computational studies on the model of coordination of the Substrates to the phenylpalladium(II)/(S,S)-chiraphos intermediate.
  • Yasunori Yamamoto, Norio Miyaura
    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 66 (3) 194 - 204 0037-9980 2008/03 [Refereed][Not invited]
     
    In this review, particular attention will be given to the synthesis of organoboron compounds via the metal-catalyzed addition and coupling reactions, and their synthetic applications in organic syntheses. The traditional methods for the synthesis of organoboron compounds are based on the reaction of trialkyl borates with Grignard or lithium reagents (transmetalation) or the addition of H-B reagents to alkenes or alkynes (uncatalyzed hydroboration). Although these methods are now most common and convenient for large-scale preparations, the metal-catalyzed reactions are advantageous in terms of efficiency and selectivity of the transformations. Hydroboration of alkenes and alkynes is one of the most studied of reactions in the synthesis of organoboron compounds and their application to organic synthesis. However, the catalyzed hydroboration to be a more interesting strategy to realize the different chemo-, regio-, diastereo-, and enantioselectivities, relative to the uncatalyzed reaction. The cross-coupling reaction of metal-boryl reagents is an alternative to the transmetalation method and perhaps a more convenient and direct protocol for the synthesis of organoboron compounds from organic halides and aromatic C-H bond. Much attention has been recently focused on organoboronic acids and their esters due to their practical usefulness for synthetic organic reactions including asymmetric synthesis, combinatorial synthesis, and polymer synthesis, molecular recognition such as host-guest compounds, and neutron capture therapy in treatment of malignant melanoma and brain tumor. New synthetic procedures reviewed in this article will serve to find further applications of organoboron compounds.
  • Yuting Wang, Shiro Shimada, Yasunori Yamamoto, Norio Miyaura
    MATERIALS RESEARCH BULLETIN 43 (2) 251 - 256 0025-5408 2008/02 [Refereed][Not invited]
     
    h-BN nano-tubes, -bamboos, and -fibers were prepared separately from borazine oligomers using an alumina porous template at different wetting times of 20 h, 40 It and 2 weeks at room temperature, respectively. The borazine oligomer in the template was transformed to the h-BN nano-materials by two-step heat-treatment at 600 and 1200 degrees C in flowing N-2. The FT-IR result confirmed the formation of BN. TEM and SEM images showed the formation of the nano-tubes in diameters 200-300 nm with thin walls about 10-20 nm thick, nano-bamboos 200-300 nm wide with knots at the separations of 0.5-1 mu m, and the nano-fibers 15-20 mu m long with fine crystallized BN particles. The mechanism for the formation of h-BN nano-tubes, -bamboos and -fibers is proposed. (c) 2007 Elsevier Ltd. All rights reserved.
  • Yuting Wang, Yasunori Yamamoto, Hajime Kiyono, Shiro Shimada
    JOURNAL OF NANOMATERIALS 1687-4110 2008 [Refereed][Not invited]
     
    An efficient approach for the preparation of good-quality boron nitride nanotubes (BNNTs) is developed. BNNTs with specific texture were prepared from ammonia borane (BH(3)NH(3)) by vapor-phase pyrolysis with the aid of a template in two independent temperature-controlled furnaces. Two kinds of BNNTs, 200-300 nm wide x 60 mu m long and 70-80 nm wide x 40 mu m long, were produced after removal of the templates. The as-produced BNNTs were heated at different temperatures in the range of 1300-1700 degrees C in NH(3). FT-IR and XPS results confirmed the formation of BN from BH(3)NH(3). Ordered arrays of BNNTs without cracks on the surface were seen using microstructural observations. The diameter and length of the BNNTs are controlled using templates with different pore sizes and thickness. The wall thickness of the nanotubes was increased by increasing the number of deposition cycles. The crystallinity of the BNNTs was improved by heating at a high temperature (1700 degrees C) in NH(3). Copyright (C) 2008 Yuting Wang et al.
  • Xiao-Qiang Yu, Yasunori Yamamoto, Norio Miyaura
    CHEMISTRY-AN ASIAN JOURNAL 3 (8-9) 1517 - 1522 1861-4728 2008 [Refereed][Not invited]
     
    The N arylation of primary and secondary aliphatic amines, anilines, and imidazoles with novel potassium aryl triolborates was carried out in the presence of a reoxidant and a catalytic amount of Cu(OAc)(2) (10mol%). Aryl triolborates were found to be better reagents than aryl boronic acids or potassium aryl trifluoroborates as the former achieved high yields under mild conditions. Coupling of primary and secondary aliphatic amines to give N-aryl amines in excellent yields was performed under oxygen atmosphere. The reactions of anilines and imidazoles to provide N-aryl anilines and N-aryl imidazoles in good yields proceeded smoothly when trimethylamine N-oxide was used as an oxidant.
  • Yasunori Yamamoto, Miho Takizawa, Xiao-Qiang Yu, Norio Miyaura
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 (5) 928 - 931 1433-7851 2008 [Refereed][Not invited]
  • Takashi Nishikata, Yuri Kobayashi, Kenya Kobayshi, Yasunori Yamamoto, Norio Miyaura
    SYNLETT (19) 3055 - 3057 0936-5214 2007/12 [Refereed][Not invited]
     
    An asymmetric 1,4-addition of arylboronic acids to (beta-(2-acylaryl)enones was carried out in aqueous isopropanol in the presence of a dicationic palladium(II) complex and HBF4. The palladium complexes of (S,S)-chiraphos gave optically active 1-aryl-1H-indenes of up to 97% ee via tandem 1,4-addition-aldol condensation.
  • Takashi Nishikata, Yasunori Yamamoto, Norio Miyaura
    CHEMISTRY LETTERS 36 (12) 1442 - 1443 0366-7022 2007/12 [Refereed][Not invited]
     
    Palladium-catalyzed 1,4-addition of arylboronic acids to unsaturated carbonyl compounds has been limitedly used for ketone and aldehyde derivatives. It was found that reaction with N-acylamides exceptionally proceeds with high yields and high enantioselectivities. A dicationic palladium-chiraphos catalyst 3 gave optically active beta-arylamides of up to 98% ee.
  • Takashi Nishikata, Yasunori Yamamoto, Norio Miyaura
    ADVANCED SYNTHESIS & CATALYSIS 349 (10) 1759 - 1764 1615-4150 2007/07 [Refereed][Not invited]
     
    The enantioselective 1,4-addition of arylboronic acids to beta-arylenones to give beta-diaryl ketones was carried out at 0-25 degrees C in the presence of a dicationic palladium(II) catalyst, [Pd(S,S-chiraphos)-(PhCN)(2)](SbF6)(2). Addition of a silver salt such as silver tetrafluoroborate [AgBF4] or silver hexafluoroantimonate [AgSbF6] (5-10 mol %) was effective to achieve high enantioselectivities at low temperatures (92-99% ee) and to reduce the catalyst loading to 0.05 mol %. The protocol provided a simple access to 4-aryl-4H-chromenes. Optically active chromenes were synthesized with up to 99% ee via dehydration of the 1,4-adducts between arylboronic acids and (2-hydroxyaryl)-alpha,beta-unsaturated ketones.
  • Takashi Nishikata, Yasunori Yamamoto, Norio Miyaura
    TETRAHEDRON LETTERS 48 (23) 4007 - 4010 0040-4039 2007/06 [Refereed][Not invited]
     
    1,4-Addition of arylboronic acid to trans-beta-arylenals proceeded smoothly in acetone-water (10/1) at 10-25 degrees C in the presence of [Pd(S,S-chirapbos)(PhCN)(2)](SbF6)(2) (0.5 mol %), AgX (X = BF4, SbF6, 10 mol %) and aqueous 42% HBF4 to afford optically active 3,3-diarylalkanals with high enantioselectivities in a range of 86-97% ee. The protocol provided a method for short-step synthesis of optically active (+)-(R)-CDP 840. (c) 2007 Published by Elsevier Ltd.
  • Kazunori Kurihara, Noriyuki Sugishita, Kengo Oshita, Dongguo Piao, Yasunori Yamamoto, Norio Miyaura
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 692 (1-3) 428 - 435 0022-328X 2007/01 [Refereed][Not invited]
     
    A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki's linked-(R)-BINOL and P(NMe2)(3) as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to alpha,beta-unsaturated carbonyl compounds. The effects of 5a and Feringa's monodentate phosphoramidite (4, R-1, R-2 = Et) on the yields and enantioselectivities were fully investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et3N, allowing the reaction to be completed at the lower temperatures than 50 degrees C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 degrees C in the presence of an [Rh(coe)(2)Cl](2)-4 (R-1, R-2 = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones (0-70% ee). On the other hand, a complex between [Rh(nbd)(2)]BF4 and 5a completed the addition to cyclic enones within 2 h at room temperature in the presence of Et3N with 86-99% yields and 96-99.8% ee. This catalyst was also effective for acyclic enones, resulting in 62-98% yields and 66-94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phosphoramidites complexes were also investigated. (c) 2006 Elsevier B.V. All rights reserved.
  • Yasunori Yamamoto, Shingo Takada, Norio Miyaura
    CHEMISTRY LETTERS 35 (12) 1368 - 1369 0366-7022 2006/12 [Refereed][Not invited]
     
    The asymmetric cross-coupling reaction of [CH3CH=CHCH2BF3]K with aryl or 1-alkenyl bromides selectively occurred at the gamma-carbon of 2-butenylborane moiety with regioselectivities in a range of 84-99%. The enantioselectivities were in a range of 77-90%ee when a palladium/CyPF-t-Bu complex was used at 80 degrees C in the presence of K2CO3 (3 equiv.) in H2O-MeOH (9/1).
  • Yasunori Yamamoto, Kazuo Miyamoto, Junko Umeda, Yasutaka Nakatani, Tetsuya Yamamoto, Norio Miyaura
    JOURNAL OF ORGANOMETALLIC CHEMISTRY 691 (23) 4909 - 4917 0022-328X 2006/11 [Refereed][Not invited]
     
    Hydroboration of terminal and internal alkenes with N,N',N"-trimethyl- and N, N', N"-triethylborazine was carried out at 50 degrees C in the presence of a rhodium(I) catalyst. Addition of dppb or DPEphos (1 equiv.) to RhH(CO)(PPh3)(3) gave the best catalyst for hydroboration of ethylene at 50 degrees C, resulting in a quantitative yield of B,B',B"-triethyl-N,N',N"-trimethylborazine. On the other hand, a complex prepared from (t-Bu)(3)P (4 equiv.) and [Rh(coe)(2)Cl](2) gave the best yield for hydroboration of terminal or internal alkenes. (c) 2006 Elsevier B.V. All rights reserved.
  • Yasunori Yamamoto, Takashi Nishikata, Norio Miyaura
    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 64 (11) 1112 - 1121 0037-9980 2006/11 [Refereed][Invited]
     
    An enantioselective synthesis of cyclic and acyclic beta-aryl ketones and esters via palladium(II)- or rhodium(I)-catalyzed 1,4-addition of Ar-[m] (m=B(OH)(2), BF3K, Si(OMe)(3), SiF3, BiAr2) to alpha,beta-unsaturated ketones or esters is described. The catalytic cycle involves transmetalation between Ar-[M] and palladium(II) or rhodium(I) complexes as the key process, the mechanism of which is discussed on the basis of characterization of the transmetalation intermediate and electronic effect of the substituents. The enantioselection mechanism and efficiency of a chiraphos ligand for structurally planar alpha,beta-unsaturated ketones are discussed on the basis of the X-ray structure of the catalyst and results of DFT computational studies on the modes of coordination of the substrates to the phenylrhodium(I)/(S, S)-chiraphos intermediate.
  • Takahiro Itoh, Toshiaki Mase, Takashi Nishikata, Tetsuji Iyama, Hiroto Tachikawa, Yuri Kobayashi, Yasunori Yarnamoto, Norio Miyaura
    TETRAHEDRON 62 (41) 9610 - 9621 0040-4020 2006/10 [Refereed][Not invited]
     
    An enantioselective synthesis of acyclic beta-diaryl ketones and esters via 1,4-addition of arylboronic acids to beta-aryl-alpha,beta-unsaturated ketones or esters is described. The complex in situ prepared from [Rh(nbd)(2)]BF4 and chiraphos was found to be an excellent catalyst to achieve high enantioselectivities in a range of 83-89% ee for the ketone derivatives and 78-94% ee for tert-butyl beta-arylacrylate derivatives. The protocol provided a catalytic method for the enantioselective synthesis of selective endothelin A receptor antagonists (7, 8) reported by SmithKline Beecham and Merck-Banyu. The enantioselection mechanism and efficiency of the chiraphos ligand for beta-aryl-alpha,beta-unsaturated ketones and esters are discussed on the basis of results of DFT computational studies on the modes of coordination of the enone substrates to the phenylrhodium(I)-(S,S)-chiraphos complex. (c) 2006 Elsevier Ltd. All rights reserved.
  • Yasunori Yamamoto, Shingo Takada, Norio Miyaura
    CHEMISTRY LETTERS 35 (7) 704 - 705 0366-7022 2006/07 [Refereed][Not invited]
     
    Cross-coupling reactions of [RCH=CHCH2BF3]K with aryl or I -alkenyl bromides occurred at the y-carbon of an allylborane moiety with perfect regioselectivities (> 99%) in the presence of a palladium/D-t-BPF complex and K2CO3 in refluxing THF.
  • T Nishikata, Y Yamamoto, ID Gridnev, N Miyaura
    ORGANOMETALLICS 24 (21) 5025 - 5032 0276-7333 2005/10 [Refereed][Not invited]
     
    Chiral complexes of [Pd(S,S-chiraphos)(PhCN)(2)](SbF6)(2) (2b) and [Pd(S,S-dipamp)(PhCN)(2)]-(SbF6)(2) (2c) catalyzed the highly enantioselective 1,4-additions Of Ar3Bi, [ArBF3]K, and ArSiF3 to cyclic and acyclic enones in aqueous methanol. The complexes catalyzed the reactions of Ar3Bi and ArSiF3 at 0-5 degrees C in the presence of Cu(BF4)(2) or ZnF2, whereas they smoothly prompted the addition of [ArBF3]K at -15 degrees C without further activation of the catalysts. The highest enantioselectivities giving beta-aryl ketones up to 99% ee were attained when using 2b for 2-cyclopentenone and acyclic (E)-enones, whereas 2c resulted in the best selectivities for 2-cyclohexenone and 2-cycloheptenone (89-96% ee). The effects on enantioselection of chiral ligands and substituents on alpha,beta-unsaturated ketones are discussed on the basis of X-ray structures of 2b and 2c as well as DFT computational studies on mechanistic aspects of the catalytic cycle.
  • Y Takahashi, Y Yamamoto, K Katagiri, H Danjo, K Yamaguchi, T Imamoto
    JOURNAL OF ORGANIC CHEMISTRY 70 (22) 9009 - 9012 0022-3263 2005/10 [Refereed][Not invited]
     
    (S)-2-(tert-Butylmethylphosphino)phenol and its methyl ether were synthesized from tert-butyldichlorophosphine via optically active phosphine-boranes as the intermediates. The former compound was used as a P/O hybrid ligand in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to acyclic enones to achieve high enantioselectivity of up to 96%.
  • Y Yamamoto, K Kurihara, N Sugishita, K Oshita, DG Piao, N Miyaura
    CHEMISTRY LETTERS 34 (9) 1224 - 1225 0366-7022 2005/09 [Refereed][Not invited]
     
    Cationic rhodium(l) complex prepared from Shibasaki's linked-BINOL and [Rh(nbd)(2)]BF4 catalyzed asymmetric 1,4-addition of arylboronic acids to enones at room temperature with high enantioselectivities up to 99.8%ee.
  • Nakamura, I, Y Mizushima, ID Gridnev, Y Yamamoto
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 127 (27) 9844 - 9847 0002-7863 2005/07 [Refereed][Not invited]
     
    A new catalytic cyclization of o-alkynylbenzaidehyde acetals 1 to the functionalized indenes 2 was found to be strictly controlled by the number of triphenylphosphine ligands on the Pd catalyst. Only complexes with three available coordination sites on Pd catalyze this reaction. Mechanistic study suggests that pi-coordination of Pd to the benzene ring is a key step controlled by the number of vacant coordination sites.
  • T Nishikata, Y Yamamoto, N Miyaura
    CHEMISTRY LETTERS 34 (5) 720 - 721 0366-7022 2005/05 [Refereed][Not invited]
     
    Asymmetric 1,4-addition of [ArBF3]K to cyclic and acyclic enones was carried out in aqueous methanol in the presence of a chiral phosphine-dicationic palladium(II) catalyst. A palladium complex of (S,S)-dipamp gave optically active beta-arylketones of up to 96 % ee for 2-cyclohexenone and 2-cycloheptenone. A palladium-(S,S)-chiraphos complex resulted in 82-97 % ee for 2-cyclopentenone and acyclic enones.
  • Y Yamamoto, R Fujikawa, T Umemoto, N Miyaura
    TETRAHEDRON 60 (47) 10695 - 10700 0040-4020 2004/11 [Refereed][Not invited]
     
    Hydroboration of terminal and internal alkenes with pinacolborane (1.2 equiv) was carried out at room temperature in the presence of an iridium(I) catalyst (3 mol%). Addition of dppm (2 equiv) to [Ir(cod)Cl](2) gave the best catalyst for hydroboration of aliphatic terminal and internal alkenes at room temperature, resulting in addition of the boron atom to the terminal carbon of 1-alkenes with more than 99% selectivities. On the other hand, a complex prepared from dppe (2 equiv) and [Ir(cod)Cl](2) resulted in the best yields for vinylarenes such as styrene. These complexes exhibited higher levels of catalyst activity and selectivity than those of corresponding rhodium complexes. (C) 2004 Elsevier Ltd. All rights reserved.
  • T Nishikata, Y Yamamoto, N Miyaura
    ORGANOMETALLICS 23 (18) 4317 - 4324 0276-7333 2004/08 [Refereed][Not invited]
     
    A high reactivity of dicationic palladium(II) complexes for transmetalation of organoboron and -silicon compounds was demonstrated in the 1,4-addition of arylboronic acids or arylsiloxanes to acyclic and cyclic enones. [Pd(dppe)(PhCN)(2)] (SbF6)(2) and nitrile-free catalysts prepared in situ from Pd(acac)(2), dppben, and Cu(BF4)(2).6H(2)O or oxidation of Pd(dba)(2) With Cu(BF4)(2).6H(2)O in the presence of dppe or dppben effectively catalyzed the reactions of arylboronic acids at room temperature and arylsiloxanes at 75degreesC. A catalytic cycle involving transmetalation between Ar-[m] (m = B(OH)(2), Si(OMe3)) and [Pd](2+) to give an Ar-[Pd](+) intermediate, insertion of an enone into the C-Pd bond, giving a palladium enolate, and finally hydrolysis with water to regenerate [Pd](2+) species was proposed. The reaction between [Pd(dppe)(PhCN)(2)](BF4)(2) (4a) and PhB(OH)(2) in the presence of PPh3 allowed the first isolation of the transmetalation intermediate [Pd(Ph)(dppe)(PPh3)] (BF4) and characterization by X-ray analysis. The reaction of a series of para-substituted arylboronic acids with 4a showed a slightly negative rho value, (-0.54), demonstrating an electronic effect that was accelerated by the donating substituents.
  • T Nishikata, Y Yamamoto, N Miyaura
    CHEMICAL COMMUNICATIONS (16) 1822 - 1823 1359-7345 2004 [Refereed][Not invited]
     
    A 1,4-addition of triarylbismuths to cyclic and acyclic enones was carried out in aqueous methanol in the presence of a chiral phosphine-dicationic palladium(II) complex. Palladium complexes of (S,S)-chiraphos or (S,S)-dipamp gave optically active beta-arylketones of up to 95% ee.
  • T Nishikata, Y Yamamoto, N Miyaura
    CHEMISTRY LETTERS 32 (8) 752 - 753 0366-7022 2003/08 [Refereed][Not invited]
     
    Catalytic 1,4-addition of arylsiloxanes to enones was carried out at 75degreesC in the presence of a dicationic palladium(II) catalyst in aqueous 1,4-dioxane. A nitrile-free complex generated in situ from Pd(dba)(2) and Cu(BF4)(2) in the presence of dppe or dppben was recognized to be the best catalyst to achieve high yields for the representative enones and enals.
  • T Nishikata, Y Yamamoto, N Miyaura
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 42 (24) 2768 - 2770 1433-7851 2003 [Refereed][Not invited]
  • Y Yamamoto, K Kurihara, A Yamada, M Takahashi, Y Takahashi, N Miyaura
    TETRAHEDRON 59 (4) 537 - 542 0040-4020 2003/01 [Refereed][Not invited]
     
    3-Alkoxy-1-alkynes 4 were hydroborated with pinacolborane (HBpin) to give 3-alkoxy-1-alkenylboronates 5. The latter gave (E)-3-alkoxyallylboronates (8: (E)-(MeO)(2)CHCH2(CH2)(n)CH2OCH=CHCH(2)Bpin, n=1-3) when they were subjected to iridium-catalyzed isomerization of the double bond. The corresponding (Z)-isomers 10 were synthesized by nickel-catalyzed isomerization of 5. Both allylboronates underwent intramolecular allylboration leading to the formation of trans-2-(ethenyl)tetrahydropyran-3-ol or 2-(ethenyl)oxepan-3-ol from 8 and the corresponding cis-isomers from 10 in the presence of Yb(OTf)(3) (20 mol%) in aqueous acetonitrile at 90degreesC. (C) 2003 Elsevier Science Ltd. All rights reserved.
  • A Takezawa, K Yamaguchi, T Ohmura, Y Yamamoto, N Miyaura
    SYNLETT (10) 1733 - 1735 0936-5214 2002/10 [Refereed][Not invited]
     
    Grignard-type addition reaction of 1-alkenylboronic acids or their esters to aldehydes or ketones were carried out in aqueous MeOH or DME in the presence of KOH (1 equivalent) and an RhCl(dppf) or Rh(OH)(dppf) catalyst (3 mol%). The utility of the protocol was demonstrated in the corresponding intramolecular reaction giving cyclic homoallylic alcohols.
  • Y Yamamoto, M Fujita, N Miyaura
    SYNLETT (5) 767 - 768 0936-5214 2002/05 [Refereed][Not invited]
     
    The rhodium-catalyzcd conjugate addition of (E)-Me3SiCH2CH=CHB(iPrO)(2) or (Z)-Me3SiCH2(C4H9)C+CHB(iPrO)(2) to enones provided a novel method for the synthesis of allylsilicone compounds possessing a carbonyl group in the same molecule which are versatile intermediates for intramolecular allylsilylation, giving cyclobutanols on treatment with Bu4NF.
  • Y Yamamoto, M Takahashi, N Miyaura
    SYNLETT (1) 128 - 130 0936-5214 2002/01 [Refereed][Not invited]
     
    The ruthenium-catalyzed olefin cross-metathesis between pinacol allylboronate, CH2=CHCH2B(O2C2Me4), and RCH=CH2 giving RCH=CHCH2B(O2C2Me4) was carried out in refluxing CH2Cl2 in the presence of an alkylidene-ruthenium complex (3 mol%).
  • T Ohmura, Y Yamamoto, N Miyaura
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 122 (20) 4990 - 4991 0002-7863 2000/05 [Refereed][Not invited]
  • T Ohmura, S Yorozuya, Y Yamamoto, N Miyaura
    ORGANOMETALLICS 19 (4) 365 - 367 0276-7333 2000/02 [Refereed][Not invited]
     
    The iridium complex generated in situ from [Ir(cod)Cl](2) and a phosphine ligand catalyzed the dimerization of terminal alkynes to give (E)-enyne, (Z)-enyne, or 1,2,3-butatriene derivatives in the presence of triethylamine. The triarylphosphine complex selectively yielded linear (E)-enynes for silylethynes, while the tripropylphosphine complex provided linear (Z)-enynes for silylalkynes or 1,2,3-butatrienes for tert-alkylethynes.
  • Y Yamamoto, R Fujikawa, N Miyaura
    SYNTHETIC COMMUNICATIONS 30 (13) 2383 - 2391 0039-7911 2000 [Refereed][Not invited]
     
    The stereoselective isomerization of unsymmetrical diallyl ethers to allyl (E)-vinyl ethers was carried out in the presence of a cationic iridium(I) catalyst. The catalyst prepared in situ by treating [Ir(cod)(PPh2Me)(2)]PF6 with hydrogen was found to be an excellent catalyst to selectively isomerize the less substituted allyl group to an (E)-vinyl ether.
  • Y Yamamoto, R Fujikawa, A Yamada, N Miyaura
    CHEMISTRY LETTERS (10) 1069 - 1070 0366-7022 1999/10 [Refereed][Not invited]
     
    The hydroboration of terminal allenes with pinacolborane was carried out at 50 degrees C in the presence of a Pt(dba)(2)/2PR(3) catalyst The formation of one of three possible monohydroboration products was regioselectively synthesized by choosing an appropriate phosphine ligand.
  • T Ohmura, Y Yamamoto, N Miyaura
    ORGANOMETALLICS 18 (3) 413 - 416 0276-7333 1999/02 [Refereed][Not invited]
     
    The stereoselective isomerization of allyl silyl ethers to (E)- or (Z)-silyl enol ethers was carried out in the presence of a cationic iridium(I) catalyst. The complex, prepared in situ by treating [Ir(cod)(2)]PF6/2PPr(3) with hydrogen, was found to be an excellent catalyst for the isomerization of primary and secondary allyl ethers in high yields. The primary allyl silyl ethers produced (E)-enol ethers and the secondary allyl ethers afforded (Z)-enol ethers with high stereoselectivity, often exceeding 99%.
  • Y Yamamoto, T Miyairi, T Ohmura, N Miyaura
    JOURNAL OF ORGANIC CHEMISTRY 64 (1) 296 - 298 0022-3263 1999/01 [Refereed][Not invited]
  • T Ohmura, Y Shirai, Y Yamamoto, N Miyaura
    CHEMICAL COMMUNICATIONS (13) 1337 - 1338 1359-7345 1998/07 [Refereed][Not invited]
     
    A cationic iridium complex, prepared via the hydrogenation of [Ir(cod)(2)]PF6-2PPr(3) is found to be an excellent catalyst for the stereoselective isomerization of primary allyl silyl ethers to (E)-enol ethers and secondary allyl ethers to (Z)-enol ethers.
  • Y Yamamoto, S Hara, A Suzuki
    SYNTHETIC COMMUNICATIONS 27 (6) 1029 - 1036 0039-7911 1997 [Refereed][Not invited]
     
    (S)-(-)-Ipsenol (2b) and (S)-(+)-ipsdienol (4b), a major component of the sex pheromone of the bark beetle, and their enantiomers (3b and 5b) were prepared enantioselectively using tartrate esters of (2-bromoallyl)boronic acid in the key step.
  • Y Yamamoto, S Hara, A Suzuki
    SYNLETT (9) 883 - & 0936-5214 1996/09 [Refereed][Not invited]
     
    Tartrate ester derivatives of 3,3-disubstituted allylborane (2) formed in situ from diisopropoxy derivatives (1) reacted with aldehydes to give the homoallylic alcohols (3) with high diastereoselectivities and good enantioselectivities.
  • S HARA, Y YAMAMOTO, A FUJITA, A SUZUKI
    SYNLETT (8) 639 - 640 0936-5214 1994/08 [Refereed][Not invited]
     
    The chiral bis(2,4-dimethyl-3-pentyl)tartrate ester of (2-(2-bromoallyl)boronic acid was directly prepared from the corresponding bis(2,4-dimethyl-3-pentyl) tartrate and (2-bromoallyl)diisopropoxyborane (1), obtained by the bromoboration reaction of allene. The enantioselective synthesis of 2-bromohomoallylic alcohols was achieved using the chiral (2-bromoallyl)boranes.
  • M SATO, Y YAMAMOTO, S HARA, A SUZUKI
    TETRAHEDRON LETTERS 34 (44) 7071 - 7074 0040-4039 1993/10 [Refereed][Not invited]
     
    3,3-Disubstituted allylborane derivatives (1c) can be prepared stereoselectively from the haloboration adducts of 1-alkynes and they afford homoallylic alcohols having quaternary carbon (2c) diastereospecifically by the reaction with aldehydes.

Books etc

  • HANDBOOK of BORON SCIENCE
    YAMAMOTO Yasunori (ContributorVol.2 Chapter 6 Transition-metal-catalyzed Reactions of Cyclic Triolborate Salts)
    World Scientific Publishing Co Pte Ltd 2018/05 (ISBN: 9781786344458) 960 157-200
  • 今日からモノ知りシリーズ トコトンやさしいクロスカップリング反応の本
    山本 靖典 (Joint work)
    日刊工業新聞 2017/05 (ISBN: 9784526077159) 160 
    クロスカップリング反応に関する、 基礎から応用までをわかり易く紹介。

Works

  • トリオールボレート塩を用いる革新的炭素-炭素結合形成反応の開発
    2010 -2012
  • キラル触媒を用いる光学活性化合物の製造
    2005 -2007
  • C-CおよびB-C結合形成における触媒プロセス
    2003 -2006
  • アリール型ホウ素化合物の直接合成法と新規触媒反応の開発
    2004 -2005
  • 有機ホウ素化合物を用いる環状化合物の合成法の開発
    2003 -2005
  • 遷移金属触媒/ジボロン系によるビニル型ホウ素化合物の高効率的合成
    2002 -2003
  • ドミノ・アリル化反応剤の開発
    2001 -2002
  • 有機ホウ素化合物を用いる触媒的有機合成
    2000 -2002
  • 水溶液中における触媒的炭素‐炭素結合形成
    2000 -2001
  • ウェルナー型ビニリデン錯体を経由するトランス-ヒドロメタル化反応
    2000 -2001
  • アリル型ホウ素反応剤の開発
    2000 -2001
  • イリジウム触媒による二重結合異性化反応を利用したアリル型ホウ素反応剤の合成
    1999 -2000
  • ホウ素‐遷移金属複合系を用いる精密有機合成
    1997 -1999
  • 芳香族有機材料開発を目的としたビアリール合成
    1997 -1998
  • アリルホウ素反応剤の合成と反応
    1996

MISC

  • 荒井 孝義, 前川 智弘, 藤岡 弘道, 佐藤 敏文, 山本 靖典  有機合成化学協会誌  71-  (7)  731  -731  2013  [Not refereed][Not invited]
  • ノーベル賞授賞式に随行して
    山本 靖典  Wako Organic Square  35-  2  -3  2011  [Not refereed][Invited]
  • YAMAMOTO Yasunori  Encyclopedia of Reagents for Organic Synthesis  2011  [Refereed][Invited]
  • 第17章 鈴木カップリングを革新するボロン酸誘導体
    山本靖典, 宮浦憲夫, 角野元重  クロスカップリング反応-基礎と産業応用-  217  -234  2010/11  [Not refereed][Not invited]
  • 環状トリオールボレート塩
    山本靖典, 宮浦憲夫  Organometallic News  72  -77  2010  [Not refereed][Not invited]
  • 第1章 鈴木カップリングを革新するボロン酸誘導体
    山本靖典, 宮浦憲夫, 角野元重  日本発ブロックバスターを目指して-創薬研究の最前線-  173  -190  2010  [Not refereed][Invited]
  • YAMAMOTO Yasunori  Encyclopedia of Reagents for Organic Synthesis  2010  [Refereed][Invited]
  • 山本 靖典  化学と教育  57-  (9)  404  -405  2009/09/20  [Not refereed][Not invited]
  • キラル触媒による光学活性化合物の製造
    山本靖典, 宮浦憲夫  M&E  36-  (3)  120  -127  2009  [Not refereed][Not invited]
  • 有機環状トリオールボレート塩を用いる遷移金属触媒反応
    山本靖典, 宮浦憲夫  Wako Organic Square  27-  2  -5  2009  [Not refereed][Not invited]
  • (2R,3R)-2,3-Bis(diphenylphosphino)butane
    Yamamoto, Y, Miyaura, N  Encyclopedia of Reagents for Organic Synthesis  1037  -1040  2009  [Refereed][Invited]
  • Boron Trichloride
    Yamamoto, Y, Miyaura, N  Electronic Encyclopedia of Reagents for Organic Synthesis  1453  -1460  2009  [Refereed][Invited]
  • 山本 靖典, 宮浦 憲夫  化学工業  60-  (1)  9  -14  2009/01  [Not refereed][Not invited]
  • Yasunori Yamamoto, Norio Miyaura  JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN  66-  (3)  194  -204  2008/03  [Not refereed][Not invited]
     
    In this review, particular attention will be given to the synthesis of organoboron compounds via the metal-catalyzed addition and coupling reactions, and their synthetic applications in organic syntheses. The traditional methods for the synthesis of organoboron compounds are based on the reaction of trialkyl borates with Grignard or lithium reagents (transmetalation) or the addition of H-B reagents to alkenes or alkynes (uncatalyzed hydroboration). Although these methods are now most common and convenient for large-scale preparations, the metal-catalyzed reactions are advantageous in terms of efficiency and selectivity of the transformations. Hydroboration of alkenes and alkynes is one of the most studied of reactions in the synthesis of organoboron compounds and their application to organic synthesis. However, the catalyzed hydroboration to be a more interesting strategy to realize the different chemo-, regio-, diastereo-, and enantioselectivities, relative to the uncatalyzed reaction. The cross-coupling reaction of metal-boryl reagents is an alternative to the transmetalation method and perhaps a more convenient and direct protocol for the synthesis of organoboron compounds from organic halides and aromatic C-H bond. Much attention has been recently focused on organoboronic acids and their esters due to their practical usefulness for synthetic organic reactions including asymmetric synthesis, combinatorial synthesis, and polymer synthesis, molecular recognition such as host-guest compounds, and neutron capture therapy in treatment of malignant melanoma and brain tumor. New synthetic procedures reviewed in this article will serve to find further applications of organoboron compounds.
  • トリオールボレート塩:金属触媒反応用に開発されたホウ素試薬
    山本靖典, 宮浦憲夫  和光純薬時報  76-  (2)  2  -5  2008  [Not refereed][Not invited]
  • Cross-coupling reactions using allyltrifluoroborate
    宮浦憲夫, 山本靖典  Organometallic News  (1)  16  -21  2007  [Not refereed][Not invited]
  • キラル配位子Me-BIPAMの開発と不斉触媒反応への応用
    宮浦憲夫, 山本靖典  Organic Square  20-  (1)  2  -4  2007  [Not refereed][Not invited]
  • Boron
    Miyaura, N, Yamamoto, Y  Comprehensive Organometallic Chemistry III  9-  146  -244  2007  [Not refereed][Not invited]
  • YAMAGUCHI KENJI, OMURA TOSHIMICHI, YAMAMOTO YASUNORI, MIYAURA NORIO  日本化学会北海道支部研究発表会講演要旨集  2003-  24  2003/07/01  [Not refereed][Not invited]
  • ホウ素
    山本靖典, 宮浦憲夫  有機金属ハンドブック<(玉尾皓平編集)>  30  -37  2003/06  [Refereed][Invited]
  • TAKEZAWA AKINORI, OMURA TOSHIMICHI, YAMAMOTO YASUNORI, MIYAURA NORIO  日本化学会講演予稿集  81st-  (2)  1158  2002/03/11  [Not refereed][Not invited]
  • 遷移金属触媒によるP-C結合形成反応の最近の進歩
    山本 靖典  Organometallic News  52  -52  2002  [Not refereed][Invited]
  • OMURA TOSHIMICHI, YAMAMOTO YASUNORI, MIYAURA NORIO  日本化学会講演予稿集  78th-  (2)  1057  2000/03/15  [Not refereed][Not invited]
  • OMURA TOSHIMICHI, YOROZUYA SHUN'ICHI, YAMAMOTO YASUNORI, MIYAURA NORIO  日本化学会講演予稿集  77th-  88  1999/09/10  [Not refereed][Not invited]

Industrial Property Rights

Awards & Honors

  • 2015/01 MDPI AG Molecules Best Paper Award 2015 3rd Prize
     Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and alpha-ketoesters. 
    受賞者: Yasunori Yamamoto;Tomohiko Shirai;Momoko Watanabe;Kazunori Kurihara;Norio Miyaura
  • 2007 日本化学会北海道支部奨励賞

Research Grants & Projects

  • 医薬品合成試薬2-ピリジントリオールボレート塩の開発
    科学技術振興機構:A-STEP(FSステージ探索タイプ)
    Date (from‐to) : 2013/08 -2014/03 
    Author : 山本 靖典
  • 文部科学省:科学研究費補助金(基盤研究(C))
    Date (from‐to) : 2010 -2012 
    Author : 山本 靖典
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(特定領域研究)
    Date (from‐to) : 2006 -2009 
    Author : Norio MIYAURA, 山本 靖典
     
    We studied B-C bond-forming reactions including borylation of C-H bonds of arenes and alkenes with iridium catalysts. A novel triolborate salts were developed for catalyzed cross-coupling or addition reactions. We developed new bidentate chiral phosphoramidites (Me-BIPAM, N-Me-BIPAM). These ligands were found to be effective for rhodium- and ruthenium-catalyzed asymmetric addition reactions of arylboronic acids to α,β-unsaturated carbonyl compounds, aldehydes and imines.
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(A))
    Date (from‐to) : 2003 -2006 
    Author : Norio MIYAURA, 山本 靖典, 石山 竜生
     
    1. Catalytic C-H BorylationDirect C-H borylation of arenes catalyzed by a transition metal complex was studied as an economical protocol for the synthesis of a variety of arylboron derivatives. Ir-catalyzed C-H borylation of arenes, heteroarenes, and benzylic positions of alkylarenes by bis(pinacolato)diboron or pinacolborane furnished aryl-, heteroaryl-, and benzylboron compounds.2. Catalytic HydroborationHydroboration of terminal and internal alkenes with pinacolborane or N, N', N"-trimethyl-and N, N', N"-triethylborazine was carried out at 25-50℃ in the presence of rhodium(I) or iridium(...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 2004 -2005 
    Author : Tatsuo ISHIYAMA, 山本 靖典
     
    1.Iridium-Catalyzed Aromatic C-H BorylationAromatic C-H borylation of arenes and heteroarenes using stoichiometric amounts of bis(pinacolate)diboron or pinacolborane was catalyzed by an iridium complex generated from 1/2[Ir(OMe)(COD)]_2 and 4,4'-di-tert-butyl-2,2'-bipyridine at room temperature in hexane and afforded the corresponding aromatic and heteroaromatic boron compounds in high yields with excellent regioselectivities. The reactions tolerated various functionalities such as halogen, carbonyl, and cyano groups or benzylic C-H bonds. A reaction mechanism may involve generation of a tr...
  • 文部科学省:科学研究費補助金(若手研究(B))
    Date (from‐to) : 2003 -2005 
    Author : 山本 靖典
     
    これまでケイ素、スズを用いた環状化合物の合成は多数報告例があるがホウ素を用いた環化反応においてはその原料となるホウ素化物の合成が困難であったためにその例は少ない。本研究課題は、クロスカップリング反応、アリルホウ素化反応、ロジウム触媒による1,4-及び1,2-付加反応など、ホウ素化合物の反応の特性を生かした環状化合物の合成法の開発を目的としている。1)アリールおよびアルケニルホウ素化合物の不斉1,4-および1,2-付加反応アリールおよびアルケニルホウ素化合物のロジウム、パラジウム触媒による不斉付加反応について検討した。ロジウム触媒を用いる付加反応では、すでにBINAP,phosphoramidite配位子を用いて高いエナンチオ選択性を達成しているが新規不斉リン配位子として2座phosphoramiditeの開発に成功した。また、パラジウム系ではジカチオン性パラジウム-chiraphos系で反応が進行し高エナンチオ選択的に反応が進行することを見出した。2)分子内にカルボニル基を有するアルケニルホウ素化合物の合成と分子内環化分子内環化を指向した種々のカルボニル基を有するアルケニルホウ素化合物の分子内1,2-付加反応を検討した。反応は[RhCl(cod)]_2触媒で効率よく進行し5員環及び6員環アリルアルコール類が立体選択的に収率良く生成した。触媒的ヒドロホウ素化、ロジウム、ジカチオ...
  • 文部科学省:科学研究費補助金(特定領域研究)
    Date (from‐to) : 2002 -2003 
    Author : 宮浦 憲夫, 山本 靖典, 石山 竜生
     
    芳香族C-H結合活性化芳香族C-H結合の活性化において反応条件を精査した結果、配位子に4,4'-di(t-butyl)-2,2'-bipyridineを用いると触媒はさらに高活性を示し、量論量の芳香族化合物を室温で直接ホウ素化できるようになった。また、反応の機構的調査よりホウ素源としてピナコールボランも利用可能となった。さらに、ジシランを用いた直接ケイ素化にも成功した。含ヘテロ芳香族化合物の直接ホウ素化も可能になり、ヘテロアリールホウ酸エステルが簡便に合成できるようなった。触媒的異性化反応を利用した短段階 γ(ω-formylalkoxy)allylboraneの合成と環化反応触媒的二重結合異性化反応は、異性化後の二重結合の立体制御が困難でこれまで有機合成に利用された例は少ないが、γアルコキシビニルホウ素化合物を選択的にγ-アルコキシアリルホウ素化合物へ変換できることをすでに見いだしている。イリジウム触媒を用いるとトランス選択的に異性化する。また、ニッケル触媒を用いるとシス選択的に異性化することが分かった。本年度は、8員環-環状エーテルを、イリジウム触媒を用いた異性化反応からトランス-8員環エーテル、ニッケル触媒を用いた異性化からジス-8員環エーテルを立体選択的に合成した。
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 2002 -2003 
    Author : Tatsuo ISHIYAMA, 山本 靖典
     
    1.Nucleophilic Borylation Reactions of Vinylic Electrophrles by Tramsition Metal Catalysts/Diboron SystemNucleophilic borylation reactions of vinylic halides or triflates with bis(pinacolato)diboron regiospesifically and stereospecifically or stereoselectrvely proceeded to afford vinylic boron compounds in excellent yields when using a combination of PdCl_2(PPh_3)_2-2PPh_3/KOPh/toluene at 50℃ or that of PdCl_2(PPh_3)_2-2PPh_3/K_2CO_3/dioxane at 80℃. The reactions tolerated various functionalities such as carbonyl and cyano groups. A catalytic cycle may involve oxidative addition of the viny...
  • 文部科学省:科学研究費補助金(奨励研究(A), 若手研究(B))
    Date (from‐to) : 2001 -2002 
    Author : 山本 靖典
     
    本研究は新規アリル型ホウ素化合物の合成を目的とし、ドミノアリル化剤として利用可能なメタルアリル金属化合物の合成法及び反応性を調査するものである。メタルアリル金属化合物はその合成が難しく、これまで報告例は限られている。さらにそのカルボニル化合物へのドミノアリル化反応への適用については、その反応性の詳しい調査もされていない。14年度はγ-ボリルアリルボラン、γ-ボリルアリルシランを用いた有機合成反応の開発を中心に行った。1.γ-ボリルアリルシランを用いた有機合成(E)-および(Z)-γ-ボリルアリルシランを用いてα,β-不飽和ケトンへのロジウム触媒による1,4-付加付加反応を調査した。反応は触媒として[Rh(cod)Cl]_2、メタノール/水混合溶媒中、100℃で進行し様々なエノンに対して付加をすることが分かった。生成物は分子内にカルボニル基を有するアリルシランとなるので、分子内環化反応に応用した。n-Bu_4NFを用いると収率良く環化し、四員環アルコールが立体選択的に得られた。また、γ-ボリルアリルシランのアルケニルボランユニットの別の利用法としてクロスカップリング反応へ応用し、新規ベンゼン環構築法の開発にも成功した。2-Chloro-1-cyclohexenecarbaldehydeにカップリング後、TiCl_4により分子内アリルシリル化反応を行うと脱水生成物であるテトラヒド...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2000 -2002 
    Author : Norio MIYAURA, 山本 靖典, 石山 竜生
     
    1)Catalytic Hydroboration of Terminal Alkynes The complex in situ generated from [M(cod)Cl]_2(M = Rh or Ir) and P'Pr_3 catalyzed a stereo- and regioselective trans-hydroboration of terminal alkynes with catecholborane or pinacolborane in the presence of Et_2N. The reaction yielded the (Z)-l-alkenylboronates with more than 96% selectivity for various terminal alkynes.2)Synthesis of Organoboronic Esters using Diboron The metal-catalyzed borylation of alkenes, alkynes, and organic electrophites with B-B compounds was developed for the synthesis of organoboronic esters from simple organic subst...
  • 文部科学省:科学研究費補助金(特定領域研究(A))
    Date (from‐to) : 2000 -2001 
    Author : 山本 靖典
     
    我々は、既に末端アルキンのヒドロホウ素化においてEt_3N存在下、ロジウム触媒により(Z)-アルケニルホウ素化合物を選択的に与える形式的なtrans-ヒドロホウ素化反応を見いだし報告しているがその詳しい反応機構は明らかになっていなかった。本年度は反応機構解明のために重水素ラベル実験、中間体のNMRによる検討をおこなった。1.重水素ラベル実験1-D-1-オクチンに対するtrans-ヒドロホウ素化反応を行った。生成したビニルボランのβ-ビニル水素はボラン由来ではなく、アルキン末端水素が転移したものが選択的に得られた。ロジウム-P^iPr_3錯体はアルキンと末端水素の転移を伴いながらvinylidene錯体を形成することが知られており、trans-ヒドロホウ素化反応がビニリデン錯体を経由して進行していることを強く示唆している。Et_3Nを添加しない場合やホスフィンをPPh_3に変えた場合には転移は観測されなかった。また、ヒドロホウ素化に活性のあるRuHCl(CO)(PPh_3)_3やシス体を与えることが確認されたRuビニリデン錯体、シス-ヒドロシリル化に有効な[RuCl_2(p-cymene)]_2をもちいてもアルキン末端水素の転移は起こらなかった。2.中間体のNMRによる検討NMRによる中間体に関する検討を行った。まず、重ベンゼン中[RhCl(coe)_2]_2にP^iPr_3、...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 2000 -2001 
    Author : Norio MIYAURA, 山本 靖典, 石山 竜生
     
    1). Development of Water-soluble Phosphine Ligand (Miyaura, Ishiyama)A Water-soluble phosphine ligand, N-(4-diphenyl-phosphino)phenylmethyl gluconanude(GLCAphos), was newly synthesized to perform the palladium-catalyzed biaryl coupling of arylboronic acids in a single aqueous media.2). Coupling and Addition Reaction of Organoboronic Acid in Aqueous Solution (Miyaura, Ishiyama, Yamamoto)The catalyst prepared from GLCAphos revealed higher activity than that synthesized from Ph_2P(m-C_6H_4SO_3Na) or P(m-C_6H_4SO_3Na)_3 for various haloarenes.The rhodium-catalyzed conjugate addition of tolylbor...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(C))
    Date (from‐to) : 2000 -2001 
    Author : Tatsuo ISHIYAMA, 山本 靖典
     
    1. Nucleophilic Borylation Reactions of Allylic Electrophiles with Diborons(1) Nucleophilic borylation reactions of allylic acetates or halides with bis(pinacolato)diboron regio-and stereoselectively proceeded at 50 degree when using a combination of Pd(dba)2/DMSO or Pd(dba)2-2AsPh3/KOAc/toluene to afford allylic boron compounds in excellent yields. The reactions also tolerated various functionalities such as carbonyl groups. A catalytic cycle may involve oxidative addition of the allylic electrophile to a palladium(0) complex, transmetalation between the diboron and a palladium(II) interme...
  • 文部科学省:科学研究費補助金(奨励研究(A))
    Date (from‐to) : 1999 -2000 
    Author : 山本 靖典
     
    本研究は、アリル型ホウ素化合物の新規合成法開発を目的とし、遷移金属触媒、とくにイリジウム、ニッケル触媒を用いた二重結合の異性化反応を利用することにより、ハイドロボレーション反応で得られるビニルホウ素化合物より一段階で目的とするアリル型ホウ素化合物への変換を達成した。さらに、イリジウム、ニッケル触媒による異性化反応の詳しい機構解明、得られたアリル型ホウ素化合物とアルデヒドなどカルボニル化合物との分子間及び分子内反応により生成するホモアリルアルコール類の立体選択性の制御、有機合成への利用を目的として調査したものである。1.シリルエノールエーテルの合成アリルシリルエーテルからシリルエノールエーテルへの異性化反応における立体選択性の発現と反応機構について詳しく調査した。その結果、[Ir(cod)_2]PF_6/2PPr_3を水素により活性化した触媒が効果的であり、1級のアリルシリルエーテルでは、アセトン、THFなど配位性の溶媒で速度論支配でトランス体を、非配位性のジクロロメタン中では速やかに熱力学的な平衡に達することがわかった。2級アリルシリルエーテルでもIr-PPr_3系は高活性を示し立体選択性はシリル基と置換基との相対的かさ高さに依存しシリル基が大きい場合はトランス体が、置換基が大きい場合はシス体が得られた。反応はπ-アリルイリジウム中間体を経由して進行しているものと考えられ、立...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 1997 -1999 
    Author : Norio MIYAURA, 山本 靖典, 石山 竜生
     
    1. The addition of 9-(alkylthio)-9-borabicyclo[3.3.1]nonane to terminal alkynes was catalyzed by Pd(PPhィイD23ィエD2)ィイD24ィエD2 to produce 9-[(Z)-2-(alkylthio)-1-Alkenyl]-9-BBN derivatives in high yields. The reactions were high regio- and stereoselective, and their conditions were sufficiently mild that a variety of functionalized alkenylborane with defined stereochemistry were readily synthesized.2. The Transition metal-catalyzed borylation of alkenes, alkynes, and organic electrophiles with B-B compounds was developed for the sysnthesis of organoboronic esters from simple organic substrates. ...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(基盤研究(B))
    Date (from‐to) : 1997 -1998 
    Author : Norio MIYAURA, 山本 靖典, 石山 竜生
     
    (1) The cross-coupling reaction of arylboronic acid with chloroarenes to give biaryls was carried out in high yields at 70-80゚C in the presence of a nickel(0) catalyst and K3P04 (3 equiv) in dioxane or benzene. The nickel(0) catalyst in situ prepared from NiCl2L (L = dppf, 2PR_3) (3-10 mol%) and 4 equiv of BuLi at room temperature was recognized to be most effective. The reaction can be applicable to a wide range of chloroarenes having an electron-withdrawing or an electron-donating group such as 4-NC, 4-CHO, 2- or 4-CO_2Me, 4-COMe, 4-NHAc, 4-Me, 4-OMe, 4-NH_2, and 4-Nme_<>. The Hammett's p...
  • 文部科学省:科学研究費補助金(奨励研究(A))
    Date (from‐to) : 1996 -1996 
    Author : 山本 靖典
     
    アリル型ホウ素化合物の調整とカルボニル化合物との有機合成反応について研究した。1-アルキンの三臭化ホウ素でのハロボレーション反応により得られる、2-ブロモ-1-アルケニボランから、有機亜鉛試薬とのクロスカップリング反応によるアルキル化、ジブロモメタンによるホモロゲーション反応を経て3,3-二置換のアリル型ボランを誘導できた。1-アルキンとしてはブチン、ヘキシン、フェニルアセチレン等が使用でき、高いジアステレオ選択性で対応する2-ブロモ-1-アルケニルボランを与えた。しかし、プロピンを用いた場合、他の1-アルキンと比べて選択性が低下することがわかった。有機亜鉛試薬としては、Me、Et、Phなど種々利用できることが明らかとなった。不斉合成を目的として得られた3,3-二置換のアリル型ボランのホウ素上のアルコキシ基を酒石酸エステル誘導体として、種々アルデヒドと反応させることにより光学活性な四級炭素を持ったホモアリルアルコールを合成した。最初に使う、アルキンと有機亜鉛試薬を選択することにより生成物の水酸基のシン-アンチの位置に自由に置換基を導入できることを見いだした。反応のジアステレオ選択性は98〜95%、エナンチオ選択性は80〜70%である。また、アリル型ホウ素化合物の新規合成法として遷移金属触媒による異性化反応を用いる方法を調査した。3-アルコキシアルキンをハイドロボレーションする...
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(一般研究(B), 基盤研究(B))
    Date (from‐to) : 1994 -1996 
    Author : Norio MIYAURA, 原 正治, 鈴木 章, 石山 竜生, 山本 靖典
     
    The addition of 9-alkylthio-9-borabicyclo [3.3.1] nonanes to terminal alkynes was catalyzed by Pd (PPh3) 4 (3mol%) to produce 9- [(Z) -2-alkylthio-1-alkenyl] -9-BBN derivatives in high yields. The synthetic utility of the reaction was demonstrated by the regio-and stereoselective one-pot synthesis of alkenyl sulfides via the palladium-catalyzed thioboration-cross-coupling sequence.Tetra (alkoxo) diboron added to alkynes in the presence of a catalytic amount of Pt (PPh3) 4 to provide stereodefined cis-bis (boryl) alkenes. Mechanistic study revealed that the oxidative addition of the B-B bond...
  • 文部科学省:科学研究費補助金(重点領域研究)
    Date (from‐to) : 1995 -1995 
    Author : 宮浦 憲夫, 鈴木 章, 山本 靖典, 石山 竜生
     
    アリールボロン酸はクロスカップリング反応によるビアリール合成に利用されている.また最近、ボロン酸基による分子認識機能なども注目されている化合物である.アリールボロン酸はアリールリチウムまたはマグネシウム試薬とホウ酸トリアルキルの金属交換反応により合成されるが、ジアリールボリン酸やトリアリールボランの副成また官能基の保護の問題があり、必ずしも容易でない場合が多い.この問題を解決する目的から、ジボロンのピナコール誘導体とハロゲン化アリールのカップリングによる直接合成方を調査した.反応条件の検討により、最適条件であるPdC12(dppf)-KOAc-DMSOの組み合わせを用いて、代表的な芳香族ハロゲン化物とのカップリングを行った.反応はハロゲン化物のパラジウム(O)に対する酸化付加段階が律速と考えられ、p-MeOやp-NMe2などの電子供与性置換基を有する芳香族ハロゲン化物との反応は、ヨウ化物でスムーズに進行するが,臭化物を用いると反応は極めて遅く実用的でない.これに対して電子吸引基(p-CO_2Me,p-COMe,p-CN,p-NO_2)を有する場合には臭化物が使用でき、原料の入手がより容易になる.また、グリニヤール法によるアリールボロン酸合成では、これらの官能基を保護する必要があるが本反応では直接合成することができより簡便である.立体障害の大きなヨードメシチレンとの反応は約1日...
  • 有機金属化合物を利用する新しい有機合成反応の開発 触媒プロセス開発
  • The highly efficient and selective organic syntheses using organometallic compounds such as transition metal-catalyzed reactions of organoboron compounds


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