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HAYASHI MasahikoGraduate School of Science / Division of ChemistryProfessor
Research activity information
■ Award- Jun. 2018 公益社団法人 新化学技術推進協会, 第7回JACI/GSC シンポジウム GSCポスター賞, Dehydrogenation of hydroquinones to benzoquinones and naphthoquinones by activated carbon under O2 atmosphere.Japan society
- The reaction of cyclohexanones with phenylhydrazines proceeded under an ethylene atmosphere in the presence of a catalytic amount of Pd/C and equimolar amount of p-toluenesulfonic acid monohydrate to afford a variety of substituted carbazoles in good to high yields. The present reaction was carried out under completely non aerobic conditions, which is in contrast with the previously reported aerobic system. This protocol was also applied to the synthesis of symmetrical carbazoles using hydrazine monohydrate in place of phenylhydrazines. The reaction will proceed in a manner similar to Fischer indole synthesis, involving a [3,3]-sigmatropic rearrangement and advancing with 1,2,3,4-tetrahydrocarbazole as an intermediate.Georg Thieme Verlag KG, Jan. 2025, SynthesisScientific journal
- American Chemical Society (ACS), Dec. 2024, The Journal of Organic Chemistry, 90(1) (1), 840 - 845Scientific journal
- Herein, novel and efficient synthesis of 3- and 2-substituted indoles starting from 2-(2-nitro-1-phenylethyl or 2-nitro-1-alkyl)cyclohexanones and 1,4-diketones, respectively using a catalytic amount of Pd/C and 1-octene system is reported.Georg Thieme Verlag KG, Nov. 2024, SynthesisScientific journal
- American Chemical Society (ACS), Nov. 2024, ACS Sustainable Chemistry & Engineering, 12(47) (47), 17328 - 17335Scientific journal
- American Chemical Society (ACS), Apr. 2024, The Journal of Organic Chemistry, 89(8) (8), 5797 - 5810, English[Refereed]Scientific journal
- American Chemical Society (ACS), Aug. 2023, The Journal of Organic Chemistry, 88(17) (17), 12276 - 12288Scientific journal
- Elsevier BV, Jun. 2023, Journal of Photochemistry and Photobiology, 15, 100176 - 100176Scientific journal
- American Chemical Society (ACS), Apr. 2023, The Journal of Organic ChemistryScientific journal
- Increasing levels of CO2 in the atmosphere is a problem that must be urgently resolved if the rise in current global temperatures is to be slowed. Chemically reducing CO2 into compounds that are useful as energy sources and carbon-based materials could be helpful in this regard. However, for the CO2 reduction reaction (CO2RR) to be operational on a global scale, the catalyst system must: use only renewable energy, be built from abundantly available elements and not require high-energy reactants. Although light is an attractive renewable energy source, most existing CO2RR methods use electricity and many of the catalysts used are based on rare heavy metals. Here we present a transition-metal-free catalyst system that uses an organohydride catalyst based on benzimidazoline for the CO2RR that can be regenerated using a carbazole photosensitizer and visible light. The system is capable of producing formate with a turnover number exceeding 8,000 and generates no other reduced products (such as H2 and CO).Mar. 2023, Nature chemistry, English, International magazineScientific journal
- Wiley, Nov. 2022, European Journal of Organic Chemistry, 2022(44) (44)Scientific journal
- The Japan Institute of Heterocyclic Chemistry, 2022, HETEROCYCLES, 104(10) (10), 1770 - 1770Scientific journal
- A C-C bond forming method was developed, whereby a furoxan ring is incorporated into various types of C-H bonds. The protocol not only offers a concise synthetic route to a variety of alkylated furoxan derivatives but also provides an efficient strategy for the insertion of various nitrogen-containing functional groups into C-H bonds via transformation of the resultant furoxan ring.Nov. 2021, The Journal of organic chemistry, 86(21) (21), 15807 - 15817, English, International magazineScientific journal
- Herein we report the first synthesis of borylfuroxans via the reaction of sulfonylfuroxans with Lewis base-ligated boranes under radical conditions. As a synthetic application, the transformation of borylfuroxans to a range of 1,2-dioximes and their derivatives is demonstrated.Jun. 2021, Organic letters, 23(11) (11), 4317 - 4321, English, International magazineScientific journal
- A novel catalytic asymmetric reaction is reported where the regiodivergent desymmetrisation of meso-azabicycloheptene via allylic oxidation using a single chiral copper catalyst produced two different, enantioenriched structural isomers in high optical purity starting from a single compound. The enantioselectivity of the two structurally isomeric compounds was enriched to >99.5% ee after derivatization.Apr. 2021, Organic letters, 23(7) (7), 2411 - 2414, English, International magazine[Refereed]Scientific journal
- The synthesis of anilines and indoles from cyclohexanones using a Pd/C-ethylene system is reported. A simple combination of NH4OAc and K2CO3 under nonaerobic conditions was found to be the most suitable to perform this reaction. Hydrogen transfer between cyclohexanone and ethylene generates the desired products. The reaction tolerates a variety of substitutions on the starting cyclohexanones.Mar. 2021, Organic letters, 23(5) (5), 1530 - 1534, English, International magazine[Refereed]Scientific journal
- Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered < -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.Feb. 2021, The Journal of organic chemistry, 86(3) (3), 2545 - 2555, English, International magazine[Refereed]Scientific journal
- Feb. 2021, JOURNAL OF ORGANOMETALLIC CHEMISTRY, 933, EnglishScientific journal
- The aminohydroxylation of methyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-unsaturated α-d-glucopyranoside proceeds in the presence of chloramine-T, OsO4 (4 mol %), (DHQ)2PHAL (5 mol %), and triethylbenzylammonium chloride (TEBAC) in both a stereoselective and a regioselective manner to produce protected methyl α-d-mannosamide as the sole product. In contrast, the reaction of methyl 2,3-unsaturated β-d-galactopyranoside under the same conditions produced a mixture of regioisomers, although the stereochemistry was perfectly controlled. The regioisomeric ratio was dependent on the nature of the protecting group and the ligand used.Jul. 2020, The Journal of organic chemistry, 85(14) (14), 9179 - 9189, English, International magazine[Refereed]Scientific journal
- Furoxans are potentially useful heteroaromatic units in pharmaceuticals and agrichemicals. However, the applications for furoxan-based compounds have been hampered due to the underdevelopment of their synthetic methods. Herein, we report a new synthetic approach for the synthesis of chloro- and bromofuroxans. The starting materials were dichloro- and dibromofuroxans, and the substituents were directly introduced to the furoxan ring in a modular fashion. The synthesized monohalofuroxans served as substrates for the installation of a second substituent to prepare further functionalized furoxans.Last, May 2020, The Journal of organic chemistry, 85(9) (9), 5959 - 5972, English, International magazine[Refereed]Scientific journal
- Utilizing radical chemistry, a new general C-C bond formation on the furoxan ring was developed. By taking advantage of the lability of furoxans, a wide variety of transformation of the synthesized furoxans have been demonstrated. Thus, this developed methodology enabled not only the modular synthesis of furoxans but also short-step transformations of carboxylic acids to a broad range of functional groups.Feb. 2020, Organic letters, 22(3) (3), 1182 - 1187, English, International magazine[Refereed]Scientific journal
- Environment-sensitive luminophoric molecules have played an important role in the fields of smart materials, sensing, and bioimaging. In this study, it was demonstrated that depending on the substituents, 9-aryl-3-aminocarbazoles can display aggregation-induced emission and solvatofluorochromism, and the operating mechanism was clarified. The application of these compounds to lipid droplet imaging and fluorescent probes for cysteamine was demonstrated.May 2019, The Journal of organic chemistry, 84(9) (9), 5535 - 5547, English, International magazine[Refereed]Scientific journal
- We found that the activated carbon-molecular oxygen system promotes the conversion of hydroquinones to benzoquinones, naphthoquinones, and anthraquinones, which are often found in natural products and pharmaceuticals. In particular, the one-pot synthesis of naphthoquinones and anthraquinones involving a Diels-Alder reaction is a useful protocol for this purpose.Mar. 2019, The Journal of organic chemistry, 84(5) (5), 2997 - 3003, English, International magazine[Refereed]Scientific journal
- Jan. 2019, Bull. Chem. Soc. Jpn., 92(1) (1), 162 - 169, English[Refereed]Scientific journal
- Carbon radicals are reactive species useful in various organic transformations. The C-X bond cleavage of organohalides by photoirradiation is a common method to generate carbon radicals in a controlled fashion. The use of organochloride substrates is still a formidable challenge due to the low reduction potential and the high dissociation energy of the C-Cl bond. In this report, we address these issues by using a nonmetal organic molecule with a relatively simple structure as a photocatalyst. In this catalyst (bis(dimethylamino)carbazole), the amino groups increase both the HOMO and LUMO energy levels, especially in the former. As a result, compared to the parent molecule, the new catalyst shows experimentally red-shifted absorption in the visible region and forms an excited state with better reducing capability. This photocatalyst was used in the reduction of unactivated aryl chlorides and alkyl chlorides in the presence of hydrogen atom donor at room temperature. The catalytic system can also be applied to the coupling of aryl chlorides with electron-rich arene and heteroarenes to affect the C-C bond-forming reactions. Our mechanistic study results support the assumption that carbon radicals are formed from the organochlorides via a single-electron-transfer step.Aug. 2018, The Journal of organic chemistry, 83(16) (16), 9381 - 9390, English, International magazine[Refereed]Scientific journal
- Aug. 2018, ChemPhotoChem, 2, 1012, English[Refereed]Scientific journal
- 2018, Tetrahedron, 74, 3642 - 3651, EnglishSynthesis of sulfonyloxy furoxans via hydroxyfuroxan ammonium salts[Refereed]Scientific journal
- 2018, Adv. Synth. Catal., 360(17) (17), 3297 - 3305, English[Refereed]Scientific journal
- Sep. 2017, The Journal of organic chemistry, 82(18) (18), 9647 - 9654, English, International magazine[Refereed]Scientific journal
- Sep. 2017, Plant & cell physiology, 58(9) (9), 1477 - 1485, English, Domestic magazine[Refereed]Scientific journal
- Aug. 2017, TETRAHEDRON LETTERS, 58(34) (34), 3337 - 3340, English[Refereed]Scientific journal
- Jun. 2017, International Symposium on Pure & Applied Chemistry 2017 (ISPAC 2017), EnglishDehydrogenative Formation of Resorcinol Derivatives Using Pd/C–Ethylene Catalytic SystemInternational conference proceedings
- We have accomplished the asymmetric synthesis of (8S,9S,10R,6Z)-trihydroxyoctadec-6-enoic acid in optically pure form and determined the absolute configuration of the natural product on the basis of the stereodetermined chiral building block 7, which was prepared by the catalytic enantioselective allylic oxidation of 4,5-epoxycyclohex-1-ene using an S-configured N,N-bidentate ligand-copper catalyst.May 2017, The Journal of organic chemistry, 82(10) (10), 5146 - 5154, English, International magazine[Refereed]Scientific journal
- May 2017, TETRAHEDRON LETTERS, 58(19) (19), 1793 - 1805, English[Refereed]Scientific journal
- Apr. 2017, Asian J. Org. Chem., EnglishStudy on the photo-induced nitric oxide-releasing ability of 4-alkoxy furoxans[Refereed]Scientific journal
- The conversion of substituted 1,3-cyclohexanediones to the alkyl ethers of resorcinol using a Pd/C-ethylene system is reported. In these reactions, ethylene works as a hydrogen acceptor. The efficient synthesis of resveratrol was achieved using this protocol as a key step. In addition, the direct formation of substituted resorcinols was carried out by adding K2CO3 into the reaction media.Mar. 2017, The Journal of organic chemistry, 82(5) (5), 2630 - 2640, English, International magazine[Refereed]Scientific journal
- Mar. 2017, ORGANIC & BIOMOLECULAR CHEMISTRY, 15(9) (9), 1964 - 1968, English[Refereed]Scientific journal
- Mar. 2017, Organic & biomolecular chemistry, 15(9) (9), 1965 - 1969, English, International magazine[Refereed]Scientific journal
- Jan. 2017, EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2017(2) (2), 409 - 413, English[Refereed]Scientific journal
- Selective Synthesis of Partially Protected d-Talopyranosides and d-Gulopyranosides via Catalytic Asymmetric Dihydroxylation: Multiplier Effects of Substrate Control and Catalyst Control.Highly selective syntheses of d-talopyranosides and d-gulopyranosides have been achieved by utilizing the multiplier effects of substrate control and catalyst control. Through the combination of an O-benzoyl-protected substrate and the AD-mix-β system, the d-talopyranoside was obtained in a ratio of 96:4. In contrast, the d-gulopyranoside was obtained in a ratio of 3:97 through the use of an O-tert-butyldimethylsilyl-protected substrate and AD-mix-α.Dec. 2016, Organic letters, 18(23) (23), 6058 - 6061, English, International magazine[Refereed]Scientific journal
- Dec. 2016, Chemical record (New York, N.Y.), 16(6) (6), 2708 - 2735, English, International magazine[Refereed]Scientific journal
- Jul. 2016, Chemistry, an Asian journal, 11(14) (14), 2006 - 10, English, International magazine[Refereed]Scientific journal
- Jul. 2016, JOURNAL OF HETEROCYCLIC CHEMISTRY, 53(4) (4), 1094 - 1105, English[Refereed]Scientific journal
- Jul. 2016, ASIAN JOURNAL OF ORGANIC CHEMISTRY, 5(7) (7), 886 - 890, English[Refereed]Scientific journal
- Jan. 2015, SYNTHESIS-STUTTGART, 47(2) (2), 187 - 192, English[Refereed]Scientific journal
- Oct. 2014, ASIAN JOURNAL OF ORGANIC CHEMISTRY, 3(10) (10), 1054 - 1057, English[Refereed]Scientific journal
- Jan. 2014, EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2014(1) (1), 244 - 253, English[Refereed]Scientific journal
- Oct. 2013, ASIAN JOURNAL OF CHEMISTRY, 25(13) (13), 7505 - 7508, EnglishEnantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Chiral Schiff Bases[Refereed]Scientific journal
- Jun. 2013, SYNTHESIS-STUTTGART, 45(11) (11), 1519 - 1523, English[Refereed]Scientific journal
- May 2013, TETRAHEDRON-ASYMMETRY, 24(9-10) (9-10), 543 - 547, English[Refereed]Scientific journal
- May 2013, TETRAHEDRON, 69(21) (21), 4221 - 4225, English[Refereed]Scientific journal
- Jul. 2012, SYNLETT, 23・1683-1685(11) (11), 1683 - 1685, English[Refereed]Scientific journal
- Jul. 2012, SYNTHESIS-STUTTGART, 44(14) (14), 2209 - 2216, English[Refereed]Scientific journal
- Jun. 2012, SYNTHESIS-STUTTGART, 44(11) (11), 1625 - 1627, English[Refereed]Scientific journal
- Feb. 2012, CHEMISTRY LETTERS, 41(2) (2), 138 - 139, English[Refereed]Scientific journal
- Feb. 2012, Carbohydrate research, 348, 91 - 4, English, International magazine[Refereed]Scientific journal
- Feb. 2012, Tetrahedron: Asymmetry, 23・959-964, EnglishEnantioselective copper-catalyzed 1,4-addition of dialkylzincs to enones using novel N,N,P-Cu(II) complex[Refereed]Scientific journal
- Jan. 2012, TETRAHEDRON, 68(4) (4), 1092 - 1096, English[Refereed]Scientific journal
- Jan. 2012, HETEROCYCLES, 84(1) (1), 569 - 575, English[Refereed]Scientific journal
- Jan. 2012, Heterocycles, 86・713-718, EnglishImidazole and Imidazoline Derivatives as N-Donor for Nickel-catalyzed Kumada-Tamao-Corriu Coupling[Refereed]Scientific journal
- Jul. 2011, The Journal of organic chemistry, 76(13) (13), 5477 - 9, English, International magazine[Refereed]Scientific journal
- Jun. 2011, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 84(6) (6), 640 - 647, English[Refereed]Scientific journal
- Feb. 2011, Carbohydrate research, 346(2) (2), 340 - 2, English, International magazine[Refereed]Scientific journal
- Dec. 2010, Heterocycles, 82・1・857-865, EnglishSimple Three Steps Synthesis of Potential Medicine for Metabolic Syndrome[Refereed]Scientific journal
- Dec. 2010, Tetrahedron Lett., 51・51・6734-6736, EnglishOxidative Transformation of Thiols to Disulfides Promoted by Activated Carbon―Air System[Refereed]Scientific journal
- Nov. 2010, The Journal of organic chemistry, 75(22) (22), 7514 - 8, English, International magazine[Refereed]Scientific journal
- Sep. 2010, Tetrahedron Lett., 51・35・4633-4635, EnglishDehydrogenation of 1,2,3,4-Tetrahydroquinoline and Its Related Compounds: Comparison of Pd/C―Ethylene System and Activated Carbon―O2 System[Refereed]Scientific journal
- Aug. 2010, Journal of Organometallic Chemistry, 695・17・2022-2029, EnglishEffect of ortho-substituents on the stereochemistry of 2-(o-substituted phenyl)-1H-imidazoline―palladium complexes[Refereed]Scientific journal
- May 2010, Pest. Biochem. Physiol., 97・1・71-75, EnglishBiota uptake of pesticides by selected plant species; the case study of Kilombero sugarcane plantations in Morogoro Region, Tanzania[Refereed]Scientific journal
- Jan. 2010, Heterocycles, 80・1・631-636, EnglishTitanium Tetraisopropoxide Promoted Reactions for the Synthesis of Substituted Coumarins[Refereed]Scientific journal
- Dec. 2009, Tetrahedron, 65・50・10459-10462, EnglishCopper(I)—2-(2'-Pyridyl)benzimidazole Catalyzed N-Arylation of Indoles[Refereed]Scientific journal
- Aug. 2009, Molecules (Basel, Switzerland), 14(8) (8), 3073 - 93, English, International magazine[Refereed]Scientific journal
- Aug. 2009, Organic letters, 11(15) (15), 3314 - 7, English, International magazine[Refereed]Scientific journal
- Apr. 2009, Bull. Chem. Soc. Jpn., 82・4・482-488, EnglishMechanistic Study of Oxidative Aromatization Using Activated Carbon—Molecular Oxygen System in the Synthesis of 2-Arylbenzazoles: Focus on the Role of Activated Carbon[Refereed]Scientific journal
- 2009, 「触媒」,持続可能社会実現のための触媒および触媒関連技術特集(触媒学会), 518-523, Japanese活性炭—酸素系による酸化反応[Refereed]Scientific journal
- 2009, 「現代化学」(東京化学同人), 34-38, Japanese活性炭が酸化反応を促進する![Refereed]Scientific journal
- Dec. 2008, Chemistry Letters, 37・12・1302-1303, EnglishConvenient Synthesis of Linear-extended Bipyridines Involving a Central Phenyl Linking Group[Refereed]Scientific journal
- Dec. 2008, Chemistry Letters, 37・12・1298-1299, EnglishCatalytic Enantioselective Reformatsky Reaction of Alkyl Iodoacetate with Aldehydes Catalyzed by Chiral Schiff Base[Refereed]Scientific journal
- Nov. 2008, The Journal of organic chemistry, 73(22) (22), 9161 - 3, English, International magazine[Refereed]Scientific journal
- Nov. 2008, Advanced Synthesis & Catalysis, 350・16・2639-2644, EnglishNovel N,N-Bidentate Ligands for Enantioselective Copper(I)-Catalyzed Allylic Oxidation of Cyclic Olefins[Refereed]Scientific journal
- Nov. 2008, Synthesis, 21・3361-3376, EnglishNew Approach for Complete Reversal of Enantioselectivity Using a Single Chiral Source[Refereed]Scientific journal
- Sep. 2008, Heterocycles, Vol76, pp715-726, EnglishOxidative Conversion of Functionalized 3,4-Dihydropyrimidin-2(1H)-ones to the Corresponding Pyrimidin-2(1H)- ones using Activated Carbon—molecular Oxygen System[Refereed]Scientific journal
- Sep. 2008, Chemistry, an Asian journal, 3(8-9) (8-9), 1465 - 71, English, International magazine[Refereed]Scientific journal
- Aug. 2008, Organic letters, 10(16) (16), 3509 - 12, English, International magazine[Refereed]Scientific journal
- Jul. 2008, Organometallics, Vol27, pp3748-3752, English2-Phenylimidazole--PdCl2 and 2-Phenylimidazoline--PdCl2 Complexes: Single Crystal and Powder X-ray Diffractometry, 1H NMR Spectra, and Comparison of Catalytic Activities in Coupling Reactions[Refereed]Scientific journal
- Mar. 2008, Synthesis, 5・770-776, EnglishVersatile and Mild Synthesis of Di- and Trisaccharidic 2,3-Enopyranosyl Cyanides by Cyanation of Per-O-acetylglycals with Trimethylsilyl Cyanide Catalyzed by Palladium(II) Acetate[Refereed]Scientific journal
- 2008, Chemical record (New York, N.Y.), 8(4) (4), 252 - 67, English, International magazine[Refereed]Scientific journal
- Dec. 2007, Journal of Solid State Chemistry, Vol180, pp3588-3593, EnglishFabrications of some kinds of 2D frameworks consisting of nanosized polyoxomolybdate anion [Mo36O112(H2O)16]8- via condensation processes[Refereed]Scientific journal
- Dec. 2007, CHEMISTRY LETTERS, 36(12) (12), 1414 - 1415, English[Refereed]Scientific journal
- Dec. 2007, ORGANOMETALLICS, 26(26) (26), 6551 - 6555, English[Refereed]Scientific journal
- Apr. 2007, ADVANCED SYNTHESIS & CATALYSIS, 349(6) (6), 833 - 835, English[Refereed]Scientific journal
- Mar. 2007, TETRAHEDRON, 63(11) (11), 2414 - 2417, English[Refereed]Scientific journal
- Feb. 2007, PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 182(2) (2), 433 - 445, English[Refereed]Scientific journal
- 2007, 有機合成化学協会誌, 65・969-976, Japanese同一の不斉源から両鏡像体を高光学純度で得る手法:触媒的不斉炭素―炭素結合形成反応を中心に[Refereed]Scientific journal
- 2007, SYNTHETIC COMMUNICATIONS, 37(10) (10), 1653 - 1657, English[Refereed]Scientific journal
- 2007, HETEROCYCLES, 74, 629 - 635, EnglishEfficient synthesis of substituted indoles and benzazoles by oxidative aromatization using activated carbon-molecular oxygen system[Refereed]Scientific journal
- Oct. 2006, TETRAHEDRON-ASYMMETRY, 17(18) (18), 2672 - 2677, English[Refereed]Scientific journal
- New chiral Schiff base as a tridentate ligand for catalytic enantioselective addition of diethylzinc to aldehydes.We have developed new chiral Schiff base catalysts for the enantioselective addition of diethylzinc reagents to aldehydes. The reaction of benzaldehyde with diethylzinc in the presence of 1 mol % of the chiral Schiff base catalyst proceeded to afford 1-phenyl-1-propanol in 96% enantiomeric excess (ee).Sep. 2006, The Journal of organic chemistry, 71(18) (18), 7091 - 3, English, International magazine[Refereed]Scientific journal
- Aug. 2006, LETTERS IN ORGANIC CHEMISTRY, 3(8) (8), 571 - 578, EnglishOxidative aromatization using molecular oxygen promoted by activated carbon[Refereed]Scientific journal
- May 2006, Tetrahedron Lett., Vol 47. No. 25, pp. 4231-4233, EnglishA Simple Synthesis of 2-Arylbenzothiazoles and its Application to Palladium-catalyzed Mizoroki-Heck Reaction[Refereed]Scientific journal
- Aug. 2005, TETRAHEDRON, 61(33) (33), 7981 - 7985, English[Refereed]Scientific journal
- Jul. 2005, TETRAHEDRON LETTERS, 46(30) (30), 4989 - 4991, English[Refereed]Scientific journal
- Aug. 2004, TETRAHEDRON, 60(32) (32), 6777 - 6783, English[Refereed]Scientific journal
- Jul. 2004, TETRAHEDRON LETTERS, 45(28) (28), 5457 - 5459, English[Refereed]Scientific journal
- May 2004, SYNTHESIS-STUTTGART, 1015-1020(7) (7), 1015 - 1020, English[Refereed]Scientific journal
- Jan. 2004, Angewandte Chemie (International ed. in English), 43(1) (1), 70 - 4, English, International magazine[Refereed]Scientific journal
- 2004, to appear in Phys. Rev.B, 未記入, EnglishSuperconductivity on a Moebius strip: numerical studies on order parameter and quasiparticles.[Refereed]Scientific journal
- Oct. 2003, The Journal of organic chemistry, 68(21) (21), 8272 - 3, English, International magazineScientific journal
- Oct. 2003, Organic letters, 5(20) (20), 3713 - 5, English, International magazineScientific journal
- Jan. 2003, Chirality, 15(1) (1), 10 - 6, English, International magazineScientific journal
- Oct. 2002, Organic letters, 4(22) (22), 3955 - 7, English, International magazine[Refereed]Scientific journal
- Aug. 2002, TETRAHEDRON LETTERS, 43(32) (32), 5645 - 5647, EnglishLewis base-catalyzed transformation of alpha,beta-unsaturated aldehydes to saturated carboxylic acids, esters and amides[Refereed]Scientific journal
- Sep. 2001, CHEMISTRY LETTERS, (9) (9), 934 - 935, EnglishTris(2,4,6-trimethoxyphenyl)phosphine (TTMPP): A novel catalyst for selective deacetylation[Refereed]Scientific journal
- Feb. 1999, TETRAHEDRON LETTERS, 40(9) (9), 1729 - 1730, EnglishC-glycosidation of unprotected D-glycals with trimethylsilyl cyanide[Refereed]Scientific journal
- The enantioselective addition of trimethylsilyl cyanide to a variety of aldehydes proceeded by the aid of a catalyst prepared in situ from titanium tetraisopropoxide [Ti(O-i-Pr)4] and chiral Schiff bases and gave the corresponding cyanohydrins in high optical yield (up to 96% e.e.). A remarkable rate enhancement was brought about by the aid of the Schiff base to the titanium alkoxide mediated silylcyanation of aldehydes. This catalyst also promoted the highly enantioselective reaction of diketene with aldehydes to give the optically active 5-hydroxy-3-oxoesters, which can be easily converted to 6-substituted-4-hydroxy lactones. These lactones are known to be a very important component of inhibitors of 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase such as compacitn and mevinolin. The chemical structure of chiral Schiff base-titanium alkoxide complexes is discussed based on their 13C NMR spectra, field desorption (FD) mass spectra, and molecular weights.The Society of Synthetic Organic Chemistry, Japan, 1994, J. Synth. Org. Chem. Jpn., 52(6) (6), 488 - 497, Japanese
- Oct. 2007, JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 65(10) (10), 969 - 976, JapaneseNew approach for complete reversal of enantioselection using Schiff base ligandBook review
- Feb. 2002, JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 60(2) (2), 137 - 144, JapaneseEnvironmentally benign oxidation of alcohols using transition metal catalystsBook review
- 日本化学会, 01 Feb. 1996, 化学と工業 = Chemistry and chemical industry, 49(2) (2), 147 - 150, JapaneseAsymmetric Carbon Carbon Bond Forming Reactions Catalyzed by Chiral Titanium Complexes-An Efficient Synthesis of Optically Active Secondary Alcohols-
- Single translation, 丸善, 2011, Japanese活性炭ハンドブックScholarly book
- Others, 化学同人, 2010, Japanese使える!有機合成反応Scholarly book
- Joint work, 丸善, Mar. 2004, Japanese第5版実験化学講座(pp.561(36))Scholarly book
- Joint work, 東京化学同人, 2004, Japanese有機合成のための触媒反応(pp.2007(4))Scholarly book
- 第50回反応と合成の進歩シンポジウム, Oct. 2024, Japanese, 日本薬学会化学系薬学部会, 神戸, Domestic conferencePd/C-エチレン系を用いたフェノール誘導体およびアニリン誘導体の合成Poster presentation
- 第53回複素環化学討論会, Oct. 2024, Japanese, 第53回複素環科学討論会, 山口, Domestic conferencePd/Cーエチレン系を用いた2-ピリジルフェノールと2-ピリジルアニリンの合成Oral presentation
- 第40回有機合成化学セミナー, Sep. 2024, Japanese, 有機合成化学協会関東支部, 新潟, Domestic conferenceベンズイミダゾリウム触媒を用いて CO2 をギ酸に還元する研究Poster presentation
- 第40回有機合成化学セミナー, Sep. 2024, Japanese, 有機合成化学協会関東支部, 新潟, Domestic conferenceヒドリド性C-H結合を持つ有機還元剤の環境調和的な光触媒化Poster presentation
- 第70回有機金属化学討論会, Sep. 2024, Japanese, 近畿化学協会有機金属部会, 大阪公立大学, Domestic conferenceボラインデンの合成と物性評価Oral presentation
- 第44回有機合成若手セミナー「明日の有機合成を担う人のために」, Aug. 2024, Japanese, 有機合成化学協会関西支部, 大阪, Domestic conference光増感剤および遷移金属を用いないベンズイミダゾリン型有機ヒドリドの光再生反応Poster presentation
- 日本化学会第103春季年会, Mar. 2023, 日本化学会, Japan, Domestic conferenceアニオン性置換基を有するカルバゾール光増感剤の合成、物性評価、光反応への応用
- 日本化学会第103春季年会, Mar. 2023, Japanese, 日本化学会, 東京理科大学, Domestic conference炭酸セシウムにより活性化されたカルバゾール光増感剤を用いたアルキルアリールエーテルのC–O結合の光還元的切断反応Oral presentation
- Sep. 2022, Japan, Domestic conferencePd/C-エチレン系を用いた置換インドールの新規合成法
- 日本化学会第101春季年会, Mar. 2021, Japaneseルテニウム触媒を用いる三重結合のジホウ素化反応
- 日本化学会第100春季年会, Mar. 2020, Japaneseニトリル配位子を有するCp*Ru錯体の合成とそれを用いた触媒反応
- 神戸大学 研究基盤センター 若手フロンティア研究会2018, Dec. 2018, Japanese, 神戸大学百年記念館, Domestic conference触媒的不斉アミノヒドロキシル化反応を用いたアミノ糖合成Poster presentation
- 日本化学会 第98春季年会 (2018), Mar. 2018, Japanese, 日本大学理工学部, Domestic conference効率的なラジカルの生成を目指した有機分子光触媒の開発Poster presentation
- 日本化学会 第98春季年会 (2018), Mar. 2018, Japanese, 日本大学理工学部, Domestic conferenceフロキサンからα-ケトエステルへの光化学的変換Oral presentation
- 日本化学会 第98春季年会 (2018), Mar. 2018, Japanese, 日本大学理工学部, Domestic conferenceN-アリールカルバゾールを基本骨格とした新規固体蛍光物質の合成Poster presentation
- 第34回有機合成化学セミナー, Sep. 2017, Japanese, 金沢市文化ホール, Domestic conference効率的な炭素ラジカルの生成を目指した有機分子光触媒の開発Poster presentation
- 第37回有機合成若手セミナー「明日の有機合成を担う人のために」, Aug. 2017, English, 同志社大学(室町キャンパス), Domestic conferenceDevelopment of Novel Photo-labile Protecting Group for Cyano GrouPoster presentation
- 第111回有機合成シンポジウム2017年【春】, Jun. 2017, Japanese, 岡山大学(島津キャンパス), Domestic conference新規フロキサン誘導体合成法の開発と光応答性一酸化窒素ドナーへの応用Oral presentation
- 第111回有機合成シンポジウム2017年【春】, Jun. 2017, Japanese, 岡山大学(島津キャンパス), Domestic conference効率的な炭素ラジカルの生成を目指した有機分子光触媒の開発Poster presentation
- The International Symposium on Pure & Applied Chemistry (ISPAC) 2017, Jun. 2017, English, Ho Chi Minh City, Vietnam, International conferenceDehydrogenative Formation of Resorcinol Derivatives using Pd/C-Ethylene Catalytic System[Invited]Invited oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conference直接的シアノ化による効率的なシアノフロキサン誘導体合成法の開発Oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conference効率的な炭素ラジカルの生成を目指した有機分子光触媒の開発Oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conference凝集誘起発光を有するカルバゾール誘導体の合成及び光物性研究Oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conference強力な脱離基を有するフロキサンの合成Oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conferenceアルキニルフロキサン合成法の開発と誘導体化の検討Oral presentation
- 日本化学会第97春季年会(2017), Mar. 2017, Japanese, 慶應義塾大学(横浜), Domestic conferencePd/C-エチレン系を用いたレゾルシノール誘導体の合成Oral presentation
- 若手フロンティア研究会2016, Dec. 2016, Japanese, 神戸大学研究基盤センター, Domestic conference効率的な炭素ラジカルの生成を目指した 有機分子光触媒の開発Poster presentation
- 第9回有機触媒シンポジウム 有機触媒研究会、研究開発専門委員会「有機分子触媒による高度分子変換技術」, Dec. 2016, Japanese, 名古屋大学, Domestic conference効率的な炭素ラジカルの生成を目指した有機分子光触媒の開発Poster presentation
- 若手フロンティア研究会2016, Dec. 2016, Japanese, 神戸大学研究基盤センター, Domestic conference効率的なシアノフロキサン合成法の開発Poster presentation
- 若手フロンティア研究会2016, Dec. 2016, Japanese, 神戸大学研究基盤センター, Domestic conference光応答性一酸化窒素ドナーの開発Poster presentation
- 若手フロンティア研究会2016, Dec. 2016, Japanese, 神戸大学研究基盤センター, Domestic conferenceアルキニル基を有するフロキサン合成法 の開発とその応用Poster presentation
- 第6回CSJ化学フェスタ2016, Nov. 2016, Japanese, タワーホール船堀, Domestic conference効率的な炭素ラジカルの生成を目指した有機分子触媒の開発Poster presentation
- 第6回CSJ化学フェスタ2016, Nov. 2016, Japanese, タワーホール船堀, Domestic conferenceハロフロキサンの新規合成法の開発と光応答性一酸化窒素ドナーへの応用Poster presentation
- 第6回CSJ化学フェスタ2016, Nov. 2016, Japanese, タワーホール船堀, Domestic conferenceアルキニル基を有するフロキサン合成法の開発とその応用Poster presentation
- 第7回サイエンスフロンティア研究発表会, Oct. 2016, Japanese, 神戸大学, Domestic conference効率的な炭素ラジカルの生成を目指した有機分子光触媒の開発Poster presentation
- 第7回サイエンスフロンティア研究発表会, Oct. 2016, Japanese, 神戸大学, Domestic conferenceアルキニル基を有するフロキサン合成法の開発とその応用Poster presentation
- 第46回 複 素環 化学 討 論会, Sep. 2016, Japanese, 金沢歌劇座, Domestic conference触媒的不斉ジヒドロキシル化反応を用いた希少糖合成Oral presentation
- 第63回有機金属化学討論会, Sep. 2016, English, 東京(早稲田大学), Domestic conferenceDehydrogenative Formation of Resorcinol Derivatives Using Pd/C―Ethylene SystemPoster presentation
- 日本化学会第96春季年会, Mar. 2016, Japanese, 日本化学会, Domestic conference触媒的不斉ジヒドロキシ化反応を用いた希少糖合成Oral presentation
- 日本化学会 第96春季年会 (2016), Mar. 2016, Japanese, 同志社大学 京田辺キャンパス, Domestic conference効率的な炭素ラジカルの生成を目指した有機分子触媒の開発Oral presentation
- 日本化学会 第96春季年会 (2016), Mar. 2016, Japanese, 同志社大学 京田辺キャンパス, Domestic conference光応答性一酸化窒素ドナーの開発Oral presentation
- 日本薬学会第136年会, Mar. 2016, Japanese, 日本薬学会, 横浜, Domestic conferenceハロフロキサンの新規合成法の開発と一酸化窒素ドナーへの応用Oral presentation
- 日本化学会 第96春季年会 (2016), Mar. 2016, Japanese, 同志社大学 京田辺キャンパス, Domestic conferenceシアノ基の光感受性保護基の開発Oral presentation
- 日本化学会 第96春季年会 (2016), Mar. 2016, Japanese, 同志社大学 京田辺キャンパス, Domestic conferenceアルキニル基を含んだフロキサン誘導体の合成Oral presentation
- 日本化学会第96春季年会, Mar. 2016, English, 日本化学会, Domestic conferenceSynthesis of 2,3-Unsaturated Sugars Using Aluminium AryloxideOral presentation
- 日本化学会第96春季年会, Mar. 2016, English, 日本化学会, Domestic conferencePractical synthesis of resorcinol derivatives using Pd C ethylene systemOral presentation
- 若手フロンティア研究会2015, Dec. 2015, Japanese, 神戸大学研究基盤センター, 神戸, Domestic conference触媒的不斉ジヒドロキシ化を用いた希少糖合成Poster presentation
- 若手フロンティア研究会2015, Dec. 2015, Japanese, 神戸大学研究基盤センター, 神戸, Domestic conferenceフラボノイド類の配糖化Poster presentation
- 若手フロンティア研究会2015, Dec. 2015, English, 神戸大学研究基盤センター, 神戸, Domestic conferencePractical synthesis of resorcinol derivatives using Pd C-ethylene systemPoster presentation
- 若手フロンティア研究会2015, Dec. 2015, Japanese, 神戸大学研究基盤センター, 神戸, Domestic conferenceD-アロースによる配糖化Poster presentation
- 第2回国際会議(兼)第7回有機触媒シンポジウム, Nov. 2014, English, 東京大学, International conferenceThe Development of a Direct Deoxygenation of AlcoholsPoster presentation
- 18th Malaysian International Chemical Congress(18MICC)2014, Nov. 2014, English, Kuala Lumpur, Malaysia, International conferenceEnantioselective Allylic Oxidation and Its Application for the Synthesis of (-)-Oseltamivir Phosphate and Oxylipin[Invited]Invited oral presentation
- Vietnam Malaysia International Chemical Congress(VMICC)2014, Nov. 2014, English, Hanoi, Vietnam, International conferenceCatalytic Asymmetric Allylic Oxidation and Its Application for the Synthesis of Some Bioactive Compounds[Invited]Invited oral presentation
- 第51回日本生物物理学会年会, Oct. 2013, English, 京都, Domestic conferenceDesign of Photo-controllable Cyclic PeptidesPoster presentation
- 日本化学会第92春季年会, Mar. 2012, Japanese, 日本化学会, 神奈川, Domestic conference銅-シッフ塩基配位子を用いたジアルキル亜鉛のエノン類への高エナンチオ選択的 1,4-付加反応Oral presentation
- 日本化学会第92春季年会, Mar. 2012, Japanese, 日本化学会, 神奈川, Domestic conference光延反応を利用した不飽和グリコシドの合成法の開発Oral presentation
- 日本化学会第92春季年会, Mar. 2012, Japanese, 日本化学会, 神奈川, Domestic conferenceグリコシドおよびその誘導体の効率的合成法の開発Oral presentation
- 活性炭研究会, Nov. 2011, Japanese, 大阪, Domestic conference活性炭を用いる酸化反応Invited oral presentation
- 2011 International Symposium on. Organometallic Chemistry, Nov. 2011, English, 大阪, International conferenceNovel Chiral N,N,P―Tridentate Ligands for Highly Enantioselective 1,4-Addition to Enones by DialkylzincsPoster presentation
- 1st International Symposium on Molecular Activation, Nov. 2011, English, Hyogo, Japan, International conferenceNovel Chiral N,N,P―Tridentate Ligands for Highly Enantioselective 1,4-Addition to Enones by DialkylzincsPoster presentation
- 第58回有機金属化学討論会, Sep. 2011, Japanese, 名古屋, Domestic conferenceNovel Chiral N,N,P―Tridentate Ligands for Highly Enantioselective 1,4-Addition to Enones by DialkylzincsPoster presentation
- The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010), Dec. 2010, English, Hawaii, USA, International conferenceHighly Enantioselective 1,4-Addition of Dialkylzincs to Enones Using Novel N,N,P-Tridentate LigandsPoster presentation
- The 6th International Symposium on Integrated Synthesis (ISIS-6), Oct. 2010, English, Kobe, Japan, International conferenceOxidative Aromatization Using Activated Carbon Oxidation SystemPoster presentation
- 第57回有機金属化学討論会, Sep. 2010, Japanese, 近畿化学協会有機金属化学討論会, 八王子, Domestic conferenceEffect of ortho-substitutents on the stereochemistry of 2-(o-substituted phenyl)-1H-imidazoline-palladium complexesPoster presentation
- 香川大学希少糖セミナー, Jul. 2010, Japanese, Domestic conference希少糖の効率的かつ効果的合成戦略Invited oral presentation
- Catalytic Asymmetric Synthesis 2010, May 2010, English, Beijing, China, International conferenceCatalytic Asymmetric Reactions Using Chiral Schiff Base-Metal Complexes[Invited]Invited oral presentation
- Catalytic Asymmetric Synthesis 2010, May 2010, English, Beijing, China, International conferenceCatalytic Asymmetric Reactions Using Chiral Schiff Base―metal Complex[Invited]Invited oral presentation
- 日本化学会第91春季年会, Mar. 2010, Japanese, 日本化学会, 大阪, Domestic conference銅(I)-2-(2’-ピリジル)ベンズイミダゾール触媒によるインドール類のN-アリール化反応Oral presentation
- 日本化学会第90春季年会, Mar. 2010, Japanese, 日本化学会, 東大阪市, Domestic conference活性炭-酸素系によるチオールからジスルフィドへの酸化反応Oral presentation
- 日本化学会第90春季年会, Mar. 2010, Japanese, 日本化学会, 大阪, Domestic conferenceタミフル合成中間体の高エナンチオ選択的合成Oral presentation
- 日本化学会第90春季年会, Mar. 2010, Japanese, 日本化学会, 東大阪, Domestic conferenceエナンチオ選択的アリル位酸化による4,5-エポキシシクロヘキサ-1-エンの不斉非対称化Oral presentation
- 日本化学会第90春季年会, Mar. 2010, Japanese, 日本化学会, 東大阪, Domestic conferenceN,N,P型三座配位子を用いたジアルキル亜鉛のエノン類への高エナンチオ選択的 1,4-付加反応Oral presentation
- 日本化学会第90春季年会, Mar. 2010, English, 日本化学会, 大阪, Domestic conference(+)および(-)-フルバスタチンとその誘導体の効率的かつ高エナンチオ選択的合成Oral presentation
- エコファーマシンポジウム, Feb. 2010, Japanese, 熊本, Domestic conference環境に負荷をかけない有機合成〜酸化反応を中心に〜[Invited]Invited oral presentation
- 11th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-11), Nov. 2009, English, Kyoto, Japan, International conferenceHighly Enantioselective 1,4-Addition of Dialkylzincs to Enones Using Novel N,N,P-Tridentate LigandsOral presentation
- 第36回有機反応懇談会, Aug. 2009, Japanese, 兵庫, Domestic conferenceSynthesis of Rare Sugar D-Allal and Studies of Oligosaccharide Synthesis Containing Rare Sugar D-Allal in TerminalPoster presentation
- 第36回有機反応懇談会, Aug. 2009, Japanese, 兵庫, Domestic conferenceOxidative Conversion of Functionalyzed 3,4-Dihydropyridine-2(1H)-ones to the Corresponding Pyrimidin-2(1H)-ones Using Activated Carbon-Molecular Oxygen SystemPoster presentation
- International Conference on Medicinal Chemistry, 2009: Frontiers in Medicinal Chemistry: Emerging Targets, Novel Candidates and Innovative Strategies, Aug. 2009, English, Bandung, Indonesia, International conferenceDevelopment of New Catalysts for the Synthesis of Optically and Biologically Active CompoundsOral presentation
- 第36回有機反応懇談会, Aug. 2009, Japanese, 兵庫, Domestic conferenceCopper-Catalyzed N-Arylation of Indoles Using 2-(2'-pyridyl)benzimidazole LigandPoster presentation
- INSTITUT TEKNOLOGI BANDUNG,Short Course in Medicinal Chemistry, Aug. 2009, English, Bandung, Indonesia, International conferenceAsymmetric Synthesis in Organic ChemistryOral presentation
- 15th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 15), Jul. 2009, English, Glasgow, UK, International conferenceHighly Enantioselective 1,4-Addition of Dialkylzincs to Enones Using Novel N,N,P-Tridentate LigandsOral presentation
- International Symposium on Chiral Compounds and Special Polymers, Jul. 2009, English, Harbin, China, International conferenceCatalytic Asymmetric Reactions Using Chiral Schiff Base—Metal Complexes[Invited]Invited oral presentation
- State Key Laboratory of Fine Chemicals, Jul. 2009, English, Dalian, China, International conferenceAsymmetric Synthesis in Organic Reactions[Invited]Invited oral presentation
- 特定領域研究「炭素資源の高度分子変換」取り纏めシンポジウム, Jun. 2009, Japanese, 京都, Domestic conference新型光学活性シッフ塩基配位子の開発と触媒的不斉合成への適用[Invited]Invited oral presentation
- 日本化学会第89春季年会, Mar. 2009, Japanese, 日本化学, 千葉, Domestic conference保護した1-エン-3-ウロースのジアステレオ選択的還元による稀少糖D-アラールの効率的合成Oral presentation
- 日本化学会第89春季年会, Mar. 2009, Japanese, 日本化学, 千葉, Domestic conference活性炭―酸素系による酸化反応を利用したピリミジン類の効率的合成Oral presentation
- 日本化学会第89春季年会, Mar. 2009, Japanese, 日本化学, 千葉, Domestic conferenceN,N,P型三座配位子を用いた銅触媒によるジアルキル亜鉛のエノン類への高エナンチオ選択的1,4-付加反応Oral presentation
- 山口大学応用分子生命科 学常盤台コロキアム, Dec. 2008, Japanese, 山口, Domestic conference触媒的不斉炭素-炭素結合の構築:アルデヒドへのエナンチオ選択的付加反応を中心にInvited oral presentation
- 第41回酸化反応討論会, Nov. 2008, Japanese, 福岡, Domestic conference活性炭―酸素系による第二級ベンジルアルコールの酸化反応Oral presentation
- 第38回複素環化学討論会, Nov. 2008, Japanese, 複素環化学討論会実行委員会, 福山, Domestic conference活性炭―酸素系による酸化反応を利用した種々の複素環化合物の効率的合成Oral presentation
- ヘテロ原子部会平成20年度第2回懇話会, Sep. 2008, Japanese, ヘテロ原子部会, 神戸, Domestic conference活性炭―酸素系を用いた芳香族複素環化合物の効率的合成Oral presentation
- 第55回有機金属化学討論会, Sep. 2008, Japanese, 大阪, Domestic conferenceEnantioselective 1,4-Addition of Dialkylzinc to Enones Using Novel N,N,P-tridentate LigandsPoster presentation
- 第35回有機反応懇談会, Aug. 2008, English, 有機反応懇談会, 大阪, Domestic conferenceNovel Chiral N,N,P―Tridentate Ligands for Highly Enantioselective Copper-Catalyzed 1,4-Addition of Dialkylzinc to EnonesPoster presentation
- 第35回有機反応懇談会, Aug. 2008, English, 有機反応懇談会, 大阪, Domestic conferenceHighly Enantioselective 1,4-Addition of Dialkylzinc to Enones Using Novel N,N,P―tridentate LigandsPoster presentation
- 第35回有機反応懇談会, Aug. 2008, English, 有機反応懇談会, 大阪, International conferenceChiral Schiff Bases as Highly Active and Enantioselective Catalysts in Catalytic Addition of Dialkylzincs to AldehydesPoster presentation
- 23rd International Conference on Organometallic Chemistry (ICOMC2008), Jul. 2008, English, Rennes, France, International conferenceDevelopment of Imidazoline and Imidazole Ligands toward Efficient Cross-Coupling ReactionsPoster presentation
- Third International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability, May 2008, English, Ohtsu, Japan, International conferenceNew Chiral N,N,P―Tridentate Ligands for Highly Enantioselective Conjugate Addition of Dialkylzinc to EnonesPoster presentation
- 日本化学会第87春季年会, Mar. 2008, Japanese, 日本化学会, 吹田, Domestic conference溝呂木-Heck反応を指向したイミダゾール、イミダゾリン配位子の創製Oral presentation
- 日本化学会第88春季年会, Mar. 2008, Japanese, 日本化学会, 東京都豊島区, Domestic conferenceトリアミンをリンカーとしたナノサイズ縮合モリブデン酸イオンの2次元フレームワークの構築Oral presentation
- Japan-Singapore Bilateral Symposium on Catalysis, Jan. 2008, English, Singapore, International conferenceCatalytic Asymmetric Carbon-Carbon Bond Forming Reactions Catalyzed by Chiral Schiff Base-Metal Complexes[Invited]Invited oral presentation
- International Symposium on Catalysis and Fine Chemicals 2007, Dec. 2007, English, Singapore, International conferenceNew Oxidation Method Using Activated Carbon and Molecular Oxygen[Invited]Invited oral presentation
- 第54回有機金属化学討論会, Oct. 2007, Japanese, 近畿化学協会有機金属化学討論会, 広島, Domestic conferenceNew Palladium―Imidazole and Imidazoline Complexes: Structure and Reactivity in Coupling ReactionPoster presentation
- 17th International Symposium on Fine Chemistry and Functional Polymers (FCFP-XVII) & IUPAC 3rd International Symposium on Novel Materials and Synthesis (NMS-III), Oct. 2007, English, Shanghai, China, International conferenceNew Palladium―Imidazole and Imidazoline Complexes: Structure and Reactivity in Coupling ReactionPoster presentation
- 17th International Symposium on Fine Chemistry and Functional Polymers (FCFP-XVII) & IUPAC 3rd International Symposium on Novel Materials and Synthesis (NMS-III), Oct. 2007, English, Shanghai, China, International conferenceCatalytic Asymmetric Carbon―Carbon Bond Forming Reactions Catalyzed Chiral Schiff Based―Metal ComplexesOral presentation
- 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis, Aug. 2007, English, Nara, Japan, International conferenceStudy of Effect on Reactivity of Azole Ligands in Palladium-Catalyzed Mizoroki-Heck ReactionPoster presentation
- Second International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability, May 2007, English, Ohtsu, Japan, International conferenceStudy of 2-(2'-Pyridyl)benzazoles Ligands Effect Based on X-ray Crystallography, 1H NMR Spectrum Analysis and its Application to Mizoroki-Heck ReactionPoster presentation
- Second International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability, May 2007, English, Ohtsu, Japan, International conferenceComplete Reversal of Enantioselection Using Oxazoline-containing Schiff Base Ligands Derived from L-Serine in Enantioselective Addition of Diketene to AldehydesPoster presentation
- 日本化学会第87春季年会, Mar. 2007, Japanese, 日本化学会, 吹田, Domestic conferenceパラジウム触媒を用いた溝呂木Heck 反応におけるアゾール型配位子効果による反応性の考察Oral presentation
- 第26回有機合成若手セミナー, Dec. 2006, Japanese, 有機合成化学協会, 大阪, Domestic conference新しい光学活性シッフ塩基配位子を用いたジアルキル亜鉛によるアルデヒドの不斉アルキル化反応Poster presentation
- 第26回有機合成若手セミナー, Dec. 2006, Japanese, 有機合成化学協会, 大阪, Domestic conferenceL-セリン由来の新規なオキサゾリン型シッフ塩基―チタン触媒を用いたジケテンのアルデヒドへの不斉付加反応におけるエナンチオ選択性の逆転現象Poster presentation
- 第26回有機合成若手セミナー, Dec. 2006, Japanese, 有機合成化学協会, 大阪, Domestic conference1H NMRスペクトル解析を用いたパラジウム-2-(2'-ピリジル)ベンゾアゾール錯体における配位子解離効果の考察Poster presentation
- The 8th International Symposium on Biotechnology, Metal Complexes and Catalysts, Nov. 2006, English, Haikou, China, International conferencePalladium Complexes Catalyzed Carbon-Carbon Bond Forming ReactionsInvited oral presentation
- The 10th International KYOTO Conference on New Aspects of Organic Chemistry, Nov. 2006, English, 近畿化学協会, Kyoto,JAPAN, International conferenceNew Chiral Schiff Base as Tridentate Ligand for Catalytic Enantioselective Addition of Diethylzinc to AldehydesPoster presentation
- 第23回有機合成化学セミナー, Sep. 2006, Japanese, 有機合成化学協会, 函館, Domestic conference新規な三座配位シッフ塩基配位子を用いた触媒的不斉アルキル化反応Poster presentation
- 第98回触媒討論会, Sep. 2006, Japanese, 日本触媒学会, 富山, Domestic conference活性炭―酸素系による酸化反応Invited oral presentation
- 第23回有機合成化学セミナー, Sep. 2006, Japanese, 有機合成化学協会, 函館, Domestic conferenceアゾール骨格を持つ窒素配位子-パラジウム錯体を用いた炭素-炭素結合形成反応Poster presentation
- 第53回有機金属化学討論会, Sep. 2006, Japanese, 近畿化学協会, 大阪, Domestic conferenceCatalytic Enantioselective Alkylation Using New Chiral Schiff Base as Tridentate LigandPoster presentation
- 第53回有機金属化学討論会, Sep. 2006, Japanese, 近畿化学協会, 大阪, Domestic conferenceCatalytic coupling reaction using N,N-bidentate palladium complexPoster presentation
- 第33回有機反応懇談会, Aug. 2006, Japanese, 有機合成化学協会, 京都, Domestic conference光学活性シッフ塩基を用いた触媒的不斉アルキル化反応と非線形現象Poster presentation
- 第33回有機反応懇談会, Aug. 2006, Japanese, 有機合成化学協会, 京都, Domestic conferenceパラジウム-窒素配位子錯体を用いた炭素-炭素結合形成反応Poster presentation
- IUPAC 2nd International Symposium on Novel Materials and Synthesis (NMS-II), Jul. 2006, English, IUPAC, 蘭州,中国, International conferenceNovel Oxidation Method Promoted by Activated CarbonInvited oral presentation
- 文部科学省科学研究費特定領域研究「炭素資源の高度分子変換」第一回公開シンポジウム, Jun. 2006, Japanese, 文部科学省, 岡山, Domestic conferenceパラジウム―イミダゾール系触媒を用いた効率的炭素―炭素結合形成反応Invited oral presentation
- 7th Tetrahedron Symposium, May 2006, English, Tetrahedron, Kyoto,JAPAN, International conferenceDirect and Practical Synthesis of 2-Arylbenzazoles Promoted by Activated CarbonPoster presentation
- 8th International Symposium on Organic Reactions, Apr. 2006, English, 入力してください, 神戸, International conferenceOxidation Using Activated Carbon-Oxygen SystemOral presentation
- 日本化学会第86春季年会, Mar. 2006, Japanese, 日本化学会, 大阪, Domestic conference活性炭―酸素系による酸化反応を利用したインドール誘導体の合成Oral presentation
- 日本化学会第86春季年会, Mar. 2006, Japanese, 日本化学会, 大阪, Domestic conferenceパラジウム触媒を用いた溝呂木-Heck反応におけるアゾール型配位子効果による反応性の考察Oral presentation
- 日本化学会第86春季年会, Mar. 2006, Japanese, 日本化学会, 大阪, Domestic conferenceL-セリン由来の新型シッフ塩基―チタン触媒を用いたジケテンのアルデヒドへの不斉付加反応におけるエナンチオ選択性の逆転現象Oral presentation
- 岡山理科大学ハイテクリサーチセンター講演会招待講演, 2006, Japanese, 入力してください, 岡山, Domestic conference環境調和型酸化反応の開発と芳香族へテロ環の合成Invited oral presentation
- 第25回有機合成若手セミナー, Nov. 2005, Japanese, 神戸大学, Domestic conference水素移動反応を利用したアルコールの酸化反応Oral presentation
- 第88回有機合成シンポジウム, Nov. 2005, Japanese, 有機合成化学協会, 日本化学会, 日本薬学会, 日本農芸化学会, 早稲田大学国際会議場, Domestic conference活性炭̶酸素系による酸化反応を利用した芳香族複素環化合物の効率的合成Oral presentation
- 第38回酸化反応討論会, Nov. 2005, Japanese, 札幌、北海道大学, Domestic conferenceニトロベンゼンを水素受容体とする水素移動反応を利用したアルコールの酸化反応Oral presentation
- 日本化学会第85春季年会, Mar. 2005, Japanese, 日本化学会, 横浜(神奈川大学), Domestic conference活性炭-酸素系による酸化反応を利用した芳香族複素環化合物の合成Oral presentation
- 日本化学会第85春季年会, Mar. 2005, Japanese, 日本化学会, 横浜(神奈川大学), Domestic conferenceニトロベンゼンを水素受容体としたアルコールの酸化反応Oral presentation
- International Conference on Topology in Ordered Phases, Mar. 2005, English, 未記入, Sapporo., Domestic conferenceFrustrated CDW states in topological crystalsOral presentation
- 日本化学会第85春季年会, Mar. 2005, Japanese, 日本化学会, 横浜(神奈川大学), Domestic conference2-プロパノール中でのチタンテトライソプロポキシドを触媒に用いる反応Oral presentation
- 日本化学会第86春季年会, 2005, Japanese, 日本化学会, 千葉、日本大学, Domestic conference光学活性シッフ塩基触媒を用いた不斉アルキル化反応Oral presentation
- 日本化学会第86春季年会, 2005, Japanese, 日本化学会, 千葉、日本大学, Domestic conference光学活性シッフ塩基-バナジウム錯体を用いたスルフィド類の不斉酸化反応Oral presentation
- 日本化学会第86春季年会, 2005, Japanese, 日本化学会, 日本大学, Domestic conference活性炭̶酸素系を用いたイミダゾリン誘導体の酸化反応Oral presentation
- 第32回有機反応懇談会, 2005, Japanese, 大阪、関西大学, Domestic conferenceパラジウム触媒を用いた水素移動反応におけるニトロベンゼンの役割Oral presentation
- 日本化学会第86春季年会, 2005, Japanese, 日本化学会, 千葉、日本大学, Domestic conferenceパラジウ-イミダゾール系触媒を用いた溝呂木-Heck反応Oral presentation
- 日本化学会第35回複素環化学討論会, 2005, Japanese, 日本化学会, 大阪、大阪大学, Domestic conferenceパラジウ-イミダゾール系触媒を用いた溝呂木-Heck反応Oral presentation
- 第25回有機合成若手セミナー, 2005, Japanese, 日本化学会, 神戸、神戸大学, Domestic conferenceパラジウ-イミダゾール系触媒を用いた溝呂木-Heck反応Oral presentation
- 第52回有機金属討論会, 2005, Japanese, 京都、同志社大学, Domestic conferenceMizoroki-Heck Reaction Using Palladium - imidazole SystemOral presentation
- 復旦大学(Fudan University) 薬学部学術講演, 2005, English, 中国, International conferenceAsymmetric Reactions Uising Novel Schiff Base-Metal ComplexesOral presentation
- 南京東南大学 (Southeast University), 2005, English, 中国, International conferenceAsymmetric Reactions Uising Novel Schiff Base-Metal ComplexesOral presentation
- 上海交通大学化学化工院学術講演, 2005, English, 中国, International conferenceAsymmetric Reactions Uising Novel Schiff Base-Metal ComplexesOral presentation
- 華東理工大学 (China East University of Science and Technology), 2005, English, 中国, International conferenceAsymmetric Reactions Uising Novel Schiff Base-Metal ComplexesOral presentation
- 中国科学院上海有機化学研究所学術講演, 2005, English, 中国, International conferenceAsymmetric Carbon-carbon Bond Forming Reactions Uising Novel Schiff Base-Metal ComplexesOral presentation
- 第24回有機合成若手セミナー, Dec. 2004, Japanese, 未記入, 京都大学薬学記念講堂, Domestic conference活性炭-酸素系による酸化反応を利用した芳香族複素環化合物の合成Oral presentation
- 第24回有機合成若手セミナー, Dec. 2004, Japanese, 未記入, 京都大学薬学記念講堂, Domestic conferenceチタンテトライソプロポキシドを促進剤に用いるKnoevenagel 型反応Oral presentation
- 白鷺セミナー, Nov. 2004, Japanese, 未記入, 大阪, Domestic conference環境調和型酸化反応の開発と芳香族へテロ環の合成Invited oral presentation
- 酸化反応討論会, Nov. 2004, Japanese, 未記入, 関西大学100周年記念館, Domestic conference活性炭_酸素系による芳香族化および酸素導入反応Oral presentation
- 複素環化学討論会, Nov. 2004, Japanese, 未記入, 金沢市観光会館, Domestic conference活性炭_酸素系による酸化反応を利用した芳香族複素環化合物の合成Oral presentation
- 神戸大学理学部サイエンスセミナー2004, Jul. 2004, Japanese, 未記入, Domestic conferenceグリーンケミストリーOthers
- 神戸大学理学部出前講義, May 2004, Japanese, 未記入, Domestic conference右と左の化学Others
- ISSP International Workshop 2003, Aug. 2003, English, 物性研究所, University of Tokyo, International conferenceSuperconducting state on a Mobius stripOral presentation
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (C), Kobe University, 01 Apr. 2021 - 31 Mar. 2024Efficient synthesis of three consecutive chiral building blocks having amino and hydroxy groups「三連続したアミノ基とヒドロキシ基をもつキラルビルディングブロックの効率的合成」の課題のもと、令和3年度は二重結合を持つエポキシド4,5-epoxycyclohex-1-eneに対して独自に開発したキラルなN,N-二座配位子(キノリル骨格を含む)と銅からなる触媒存在下に、tert-ブチル過安息香酸を酸化剤に用いてアリル位酸化反応を行なった。 その結果、(3S,4S,5S)-3-benzoyl-4,5-epoxycyclohex-1-eneが84%eeの光学純度で得られた。得られたこの化合物を一旦、ベンゾイル基を脱保護したのち、p-ニトロベンゾイル基へと変換し、再結晶をすることで光学純度を100%ととした。エポキシドを水で開環することで、ヒドロキシ基が三連続のキラルビルディングブロックの合成を達成した。三つのヒドロキシ基の隣接部分はいずれもトランス(アンチ)であった。さらに、アジ化ナトリウムで開環することによってヒドロキシ基、ヒドロキシ基、アミノ基の順で交互にトランスで得られた。 以上は、アリル位に酸素導入を行った結果得られたものである。次にアリル位にアミノ源を導入することで、ヒドロキシ基、ヒドロキシ基、アミノ基およびヒドロキシ基、アミノ基、アミノ基が得られることも確認した。立体はいずれも互いにトランスで、光学純度は100%であった。さらに、残った二重結合をオゾン酸化することによって鎖状化合物への変換も行なった。得られた化合物は鎖状のジアルデヒドのため酸化されやすく、速やかにアセタール保護することで有用化合物合成の中間体として用いることができる。
- 学術研究助成基金助成金/挑戦的萌芽研究, Apr. 2015 - Mar. 2017, Principal investigatorCompetitive research funding
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (B), Kobe University, 01 Apr. 2012 - 31 Mar. 2016Preparation and Properties of Ionic Liquids from Metal ComplexesFunctional metal-containing ionic liquids were synthesized from various cationic metal complexes. First, ionic liquids exhibiting vapochromic, magnetic, and other properties were developed from chelate complexes. Second, a series of ionic liquids were synthesized from metallocenium complexes, and their physical properties and chemical reactivities investigated. Correlations between the crystal structures and thermal properties of metallocenium salts were also investigated.
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (B), Kobe University, 2009 - 2011Metallocenium Ionic Liquids: Preparation, Electronic Properties, and Chemical ReactivitiesA series of metal-containing ionic liquids that are based on metallocenium cations were developed. The thermal properties, magnetic properties, and chemical reactivities of these ionic liquids were investigated.
- 科学研究費補助金/新学術領域研究, 2011, Principal investigatorCompetitive research funding
- 科学研究費補助金/基盤研究(B), 2011, Principal investigatorCompetitive research funding
- 科学研究費補助金/基盤研究(B), 2010Competitive research funding
- 科学研究費補助金/特定領域研究, 2007, Principal investigatorCompetitive research funding
- 科学研究費補助金/特定領域研究, 2006, Principal investigatorCompetitive research funding
- 科学研究費補助金/基盤研究(B), 2006Competitive research funding
- 科学研究費補助金/基盤研究(B), 2005, Principal investigatorCompetitive research funding
- 日本学術振興会, 科学研究費助成事業, 特定領域研究, 神戸大学, 2002 - 2003新規なN,P-型キレート金属錯体を用いた無保護グルカール類の立体選択的変換反応無保護グルカールのアリルアルコールを選択的に酸化して得られるエノン体(ウロース)をグリコシル供与体に用い、触媒量のパラジウム触媒存在下、シアン化トリメチルシリルを作用させると、立体選択的1,4-付加が進行し、対応する3-ケト-1-シアノ糖が高収率かつ高いα選択性でもって得られた。本反応でパラジウム触媒として2価のパラジウムの他、0(ゼロ)価のパラジウムを用いることもできる。グルカールのグリコシル化では、2価のパラジウムのみが触媒活性をもつことと対照的である。そこで、酢酸パラジウムにポスフィン配位子を添加することで、α/β=94/6まで向上させることができた。さらに、本反応で用いたエノン体合成の際に見い出した、Pd/C触媒を用いる酸化反応をピラゾリンからピラゾールへの芳香族化に適用できることを見い出した。その後、これらのピラゾリンは、酸化剤であるPd/Cを一切用いなくとも、活性炭だけで酢酸あるいはキシレン中,加熱するのみで,対応するビラゾールへと変換されることがわかった。本反応では酸素が必須である。活性炭が効率的に酸素を吸着し,反応を促進していると考えられる。この反応はパラジウム触媒-エチレン系と異なり,水素移動型(脱水素)の反応ではなく,酸素の取込みの後,水が抜ける脱水型の反応である。 活性炭-酸素系はジヒドロピリジンからピリジンへの変換,アリールベンズオキサゾール,アリールイミダゾール類の合成(Org.Lett.,5,3713(2003)),アントラセン類の合成(J.Org.Chem.,68,8272 (2003))においても良好な結果を与えた。これらの変換は従来,過マンガン酸や硝酸あるいはDDQを用いて酸化していたが、本法により環境調和型の酸化が実現できた。
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (B), Kobe University, 2001 - 2003Development of dehydrogenation reaction using palladium catalyst and ethylene systemRecently reported oxidation process of alcohols using molecular oxygen as an oxidizing agent in the presence of catalytic amount of transition metals such as copper, ruthenium, and palladium compounds will be reviewed. Oxidation of alcohols based on hydrogen transfer reaction between alcohols and simple olefins such as ethylene is also described. That is, some benzylic and allylic alcohols can be converted into the corresponding carbonyl compounds using a catalytic amount of palladium on activated carbon (Pd-C) under ethylene atmosphere. The combination of Pd(OAc)2 and vinyl acetate also works efficiently. Selective oxidation of hydroxy groups on carbohydrates (D-glycals) and steroids as well as simpler systems has been achieved. Oxidative aromatization reaction has been also realized by Pd-C/acetic acid/02 system. 1,3,5-Trisubstituted pyrazolines and Hantzsch 1,4-dihydropyridines were converted into the corresponding pyrazoles and pyridines effectively by the treatment of a catalytic amount of Pd/C in acetic acid under oxygen atmosphere. Direct synthesis of 2-arylbenzoxazoles from 2-aminophenols and aldehydes was achieved in the presence of activated carbon (Darco KB) under oxygen atmosphere. These environmentally benign oxidation methods have potentialities to replace the conventional stoichiometric chromium and other metal oxidizing agents.
- 日本学術振興会, 科学研究費助成事業, 特定領域研究(A), 神戸大学, 2001 - 2001新規なN,P-型キレート金属錯体を用いた無保護グルカール類の立体選択的変換反応無保護グルカールに触媒量(1mol%)のPd(OAc)_2存在下、シアン化トリメチルシリルを作用させたところ、2,3-不飽和-1-シアノ糖が99%収率,α/β=75/25で得られた。この系に、ホスフィン配位子を添加したところ、反応は進行しなくなった。一方、無保護グルカールのアリルアルコールを選択的に酸化して得られる無保護ウロースに、1mol%のPd(OAc)_2存在下、シアン化トリメチルシリルを作用させたところ、3-ケト-1-シアノ糖が96%収率,α/β=88/12で得られた。この系に、P(o-tol)_3を添加したところ、α/β=94/6(82%収率)にまでα選択性が向上した。このように配位子の添加がC-グリコシル化反応の立体選択性に影響を与えうることがわかった。また、これらの結果から無保護グルカールの場合は、零価のパラジウムでは触媒活性がなく、2価のパラジウムがルイス酸的に働いていること、それに対して、無保護ウロースの場合には、零価のパラジウムでも活性があることから、別の機構で進行していることが明らかとなった。さらに、ウロースの場合には配位子の添加による立体化学制御が期待できることもわかった。 上記反応において、無保護グルカールからウロース(エノン体)への酸化の際に開発したPd/C触媒を用いる脱水素化反応を複素環化合物に適用した。すなわち、ピラゾリンからピラゾール、ジヒドロピリミジンからピリミジンへの変換を試みたところ、効率よく脱水素化が進行した。さらに、ピラゾリンからピラゾールへの変換はパラジウム触媒なしでも進行し、この場合には、脱水素化でなく、脱水反応が起きていることも明かとした。
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research on Priority Areas (B), Kyushu University, 1998 - 2000Stereocontrol utilizing intermolecular interactionDynamic control of intermolecular interaction is indispensable for achieving highly stereocontrolled reactions. We have developed various new stereocontrolled reactions on the basis of new knowledge on the factors controlling intermolecular reactions. (1) Study with metallosalen complexes The X-ray structural analysis of metallosalen complexes clarified that conformation of the salen ligands is strongly influenced by weak-bond interactions such as OH-π and CH-π interactions and by the presence or absence of a donor ligand. With this knowledge, highly cis- and enantio-selective cyclopropanation was achieved for the first time. Furthermore, new type of asymmetric catalysts activated by photo-irradiation were introduced and, with these complexes, catalytic asymmetric oxidation using molecular oxygen as the terminal oxidant was developed. (2) New methodologies for acyclic stereocontrol Stereospecific and regioselective epoxide-ring opening using new aluminum and borane reagents enabled efficient construction of consecutive asymmetric centers. High efficient construction of chiral quaternary carbons was also developed. With these reactions as key steps, various natural products of complex architectures were synthesized in a highly straightforward manner. (3) Asymmetric induction based on dynamic chirality of enolate structure Direct α-alkylation of optically active α-amino acids was achieved in an enantiospecific manner in the absence of any external chiral sources. Newly introduced nucleophylic catalyst bearing p-aminopyridine moiety enabled highly enantiomer-differentiating acylation. The origin for the observed selectivity was attributed to enantiomer-selective acceleration. (4) Transition metal catalysts in stereoselective carbohydrate synthesis Various carbohydrate derivatives were synthesized efficiently from protected and unprotected glucals by using transition metal catalysts. (5) Desymmetrization of meso-diols and memory of chirality in carbenium ion Asymmetric desymmetrization of meso-diols was achieved efficiently by mono-acylation using chiral binaphthyltin dibromide as a catalyst. Optically acive α-amino acids were converted into optically active aminals via the corresponding acylinium ions in the absence of any external chiral sources. These results disclosed that memory of chirality can be observed in the reactions proceeding through a carbenium intermediate.
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Scientific Research (C), Yamaguchi University, 1998 - 1999Catalytic asymmetric synthesis of optically active amines and their derivativesFor the development of the asymmetric synthesis of optically active amines and their derivatives, we examined the enanioselective addition of trimethylsilyl cyanide to a variety of N-substituted imines. At first, we investigated the reaction catalyzed by chiral Schiff base-titanium alkoxide complexes which was very effective for enantioselective trimethylsilylcyanation of aldehydes. We found that by using chiral titanium complexes, high chemical yield was attained, but only unsatisfied optical yield (20% ee) was obtained. The chiral titanium complex bearing chiral binaphthol derivatives was also found to give only low optical yield. Then we examined the reaction catalyzed by cationic chiral BINAP- palladium complex. By using complex of in-situ preparation and isolated one, low optical yield was obtained in both cases though chemical yield was high. Based on the above results we changed the strategy for the synthesis of optically active amines, that is, catalytic asymmetric allylic amination catalyzed by palladium complexes. We have succeeded in the synthesis of novel palladium catalyst having P, N-bidentate ligands. These new catalyst was found to have high catalytic activity and enantioselectivity in catalytic allylic alkylation. The optical yields of the allylic alkylation products were over 80% ee. At present, the asymmetric amination is being examined.
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for General Scientific Research (C), Yamaguchi University, 1994 - 1995Enantioselective Reaction of Diketene to Aldehydes Promoted by Chiral Titanium ComplexesOptically Active 5-hydroxy-3-oxoesters can be converted into 6-substituted 4-hydroxy lactones which are common structural components of compactin and mevinolin known as inhibitors of 3-hydroxy-3-methylglutaryl Coenzyme A (HMG-CoA) reductase. W e recently succeeded in the highly efficient preparation of optically active 5-hydroxy-3-oxoesters by enantioselective reaction of diketene with aldehydes promoted by novel chiral Schiff basetitanium alkoxide complexes. This new procedure provides an efficient method for the synthesis of optically active 5-hydroxy-3-oxoesters in up to 92% enantiomeric excess (ee).
- Japan Society for the Promotion of Science, Grants-in-Aid for Scientific Research, Grant-in-Aid for Developmental Scientific Research (B), YAMAGUCHI UNIVERSITY, 1991 - 1992The Production of Chiral beta-Aminoalcohols to be excellent catalysts for the synthesis of optically active sec-alcohols.The synthetic methods of optically active sec-alcohols are knwon that asymmetric reductions of unsymmetrical ketones or the asymmetric alkylation of aldehydes are useful methods. The author found the asymmetric alkylation method of aldehydes with dialkylzinc catalyzed by beta-aminoalcohols in 1983. For the first time we studied the synthetic method of optically active 2-hydroxy-3,3-dimethyl-butylamine which was excellent catalysts for alkylation of aldehydes. High yield production ofmonobromination or monochlorination of pinacolone was succeeded by the reaction at 0゚C.The reduction of monohalogeno-pinacolone was performed by NaBH_4 in MeOH-H_2O,followed by treatment of alkalline to give t-butylethylene oxide. Thus, obtained t-butylethylene oxide was reacted with N-magnesium salt of sec-amines to give N-dialkyl-2-hydroxy-3,3-dimethyl-1-butylamines in high yield. By this method a variety of beta-aminoalcohols could be prepared. Rac-beta-aminoalcohols was resolved by Sharpless asymmetric oxidation which was very useful method for resolving beta-aminoalcohols. The production of optically active beta-amino-alcohols in industrial scale is now in pending, because the demand of the products is now in step of researching.
- 日本学術振興会, 科学研究費助成事業, 一般研究(B), 山口大学, 1990 - 1991不斉増幅現象の研究不斉増幅現象は本申請者の発見した不斉反応における重要な現象の一つである。最初の発見はフランスのKagan教授によるアリルアルコ-ルの不斉エポキシ化反応においてであったが、増幅と呼べるものではなかった。本申請者が発見した光学活性βーアミノアルコ-ルを触媒成分とするジアルキル亜鉛のアルデヒド類への不斉付加反応において、極めて光学純度の低い触媒より光学純度の大変高いアルコ-ル類を得る反応を発見し、この現象を不斉増幅と命名した。この不斉増幅現象の起因を研究して、さらに発展させるのがほんの研究の目的であった。 1。光学活性βーアミノアルコ-ルとジエチル亜鉛のモル比1:1の反応物を溶液中の分子量測定およびNMRスペクトルによって研究をした結果、この反応物は溶液中2量体に会合していることが分かった。しかしラセミのーアミノアルコ-ルとジエチル亜鉛の反応物も同様の研究により2量体であるが、光学活性体からの物とは全く異なった構造を有するメゾ2量体であることが判明した。このメゾ2量体は触媒活性が大変弱いことより、光学活性2量体のみが会合を解き、触媒として働くことが結論された。 2。チタニウムテトライソプロポキシド、Ti(OiPr)_4、と酒石酸エステルとを組み合わせるSharpless触媒を用いて、アルデヒド類の高度な不斉シリルシアノ化反応を触媒量的に進行させる反応を、世界ではじめて本申請者は成功させた。この反応においても本申請者は不斉増幅現象を見いだしイギリス化学会の雑誌(J.Chem.Soc.)に報告した。特に、この反応は医薬品の分野における抗生物質の原料合成、農薬合成および液晶合成および液晶成分の合成等に適応できるので、企業関係からの問い合わせが殺到している。この反応においても、触媒の会合が重要な鍵であることを、触媒のマススペクトルの研究から明かにした。
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