OKADA Yoshiharu

Researcher Information

Degree

• Doctor of Engineering（Kyushu Institute of Technology）

J-Global ID

• 200901056083670723

Research Interests

• 有機合成   Asymmetric Synthesis   

Research Areas

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

Academic & Professional Experience

• 2013/04 - Today  Kindai UniversityFaculty of Engineering, Department of Biotechnology and Chemistry 准教授
• 2007/04 - 2013/03  Kindai UniversityFaculty of Engineering准教授
• 2003/04 - 2007/03  Kindai UniversityFaculty of Engineering助教授
• 1995 - 2003  Kindai UniversityFaculty of Engineering
• 1993 - 1995  Kyushu Institute of Technology
• 1993 - 1995  Kyushu Institute of Technology, Research
• Assistant

Education

•        - 1982  Kyushu Institute of Technology  School of Engineering  工業化学科
•        - 1982  Kyushu Institute of Technology  Faculty of Engineering

Association Memberships

• イギリス王立化学会   アメリカ化学会   日本油化学会   有機合成化学協会   日本化学会   

Published Papers

• Convenient Synthesis and Physiological Activities of Flavonoids in Coreopsis lanceolata L. Petals and Their Related Compounds

  OKADA Yoshiharu

  Molecules 23 (7) 1671  2018/07 [Refereed][Invited]
  
• Relationship between the Oligosaccharide Content in Cooked Rice and Its Taste Characteristics

  横野一歩; 渡邉義之; 高津地志; 藤田明子; 岡田芳治; 野村正人

  Journal of the Japanese Society of Taste Technology 美味技術学会 15 (2) 15 - 20 2186-7224 2017/01 [Refereed]
  
• Flavor Components in the Steam Generated during Rice Cooking and their Antioxidant Potential

  村上結城; 藤田明子; 渡邉義之; 岡田芳治; 野村正人

  Journal of the Japanese Society of Taste Technology 美味技術学会 14 (1) 5 - 10 2186-7224 2015/07 [Refereed]
  
• Convenient Synthesis of 1-(Trimethylsilyl)- and 1-(Trimethylstannyl)Vinylphosphonates and Their Synthetic Application

  Yoshiharu Okada; Riho Urushihara; Masato Nakamoto

  PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS TAYLOR & FRANCIS LTD 190 (5-6) 922 - 924 1042-6507 2015/06 [Refereed]
   

  Dimethyl 1,1-bis(trimethylsilyl)methylphosphonate was succeeded to react with aromatic aldehydes in the presence of methyl benzoate as additive to give the corresponding vinylphosphonates in moderate yields. Michael addition and subsequent Peterson olefination reaction of dimethyl (Z)-2-(3,4-methylenedioxyphenyl)-1-(trimethylsilyl)vinylphosphonate with 3,4,5-trimethoxyphenyllithium and crotonaldehyde afforded the corresponding (2E,4E)-1-(3,4,5-trimethoxyphenyl)-1-(3,4-methylenedioxyphenyl)-2-(dimethylphosphono)hexa-2,4-diene in 36% yield.
• Evaluation of the fatty acid composition of the seeds of mangifera indica L. and their application

  Shuhsien Wu; Megumi Tokuda; Ayaka Kashiwagi; Atsushi Henmi; Yoshiharu Okada; Shinya Tachibana; Masato Nomura

  Journal of Oleo Science Japan Oil Chemists Society 64 (5) 479 - 484 1347-3352 2015 [Refereed]
   

  Mango (Mangifera indica L.), an edible fruit, is one of the main agricultural products in many tropical regions. Mango varieties differ in not only fruit shape but also aroma, which is an important characteristic. Although the fruit has many uses, the seeds are discarded as waste. Therefore, this study aimed to estimate the fatty acid content of seed oil of mangoes from different cultivation areas (Miyazaki, Japan, and Taiwan), and to evaluate their application in cosmetics. Five fatty acids were identified in the mango seed oil. Oleic acid and stearic acid were the principal components of mango seed oil obtained from Miyazaki (46.1% and 39.8%, respectively) and Taiwan (43.7% and 40.1%, respectively). As a cosmetic ingredient, mango seed oil showed good deodorizing effect on both 2-nonenal and isovaleric acid. The results indicated the potential applications of mango seed oil in the cosmetic industry.
• Physiological Activity of Chinese Lichen (Gyrophora esculenta) Component, Methyl 2,4-Dihydroxy-6-methylbenzoate and the Related Compounds

  Shuhsien Wu; Zhendong Zhao; Yoshiharu Okada; Yoshiyuki Watanabe; Toshiyuki Takahata; Toshio Inoue; Eiji Otsubo; Jing Wang; Yanju Lu; Masato Nomura

  ASIAN JOURNAL OF CHEMISTRY ASIAN JOURNAL OF CHEMISTRY 26 (3) 702 - 708 0970-7077 2014/02 [Refereed]
   

  It was confirmed that there was a higher expression of antioxidant potential in methyl 2,4-dihydroxy-6-methylbenzoate (orsellinic acid methyl ester) (2), which was isolated from methanol extract oil of Chinese lichen Gyrophora esculenta rather than from commercialized ascorbic acid. Taking this into account, 4 types of compounds-(4-7) which are known to be related to compound (2)-have been synthesized by using 2,4-dihydroxy benzoic acid (3) as starting material. After that, some physiological activity tests on these compounds have been conducted in the following aspects: antioxidant potential, cytotoxicity, cytokine suppressant effect and histamine liberation inhibition and the effects have been evaluated, respectively. The result shows that (2) and methyl 2,4-dihydroxybenzoate (4) showed high radical expression in both antioxidant potential and histamine liberation inhibition. It was also found that none of these compounds expresses cytotoxicity.
• Isolation and identification of flavonoids from Coreopsis lanceolata L. petals

  Yoshiharu Okada; Mari Okita; Yoshihiro Murai; Yuka Okano; Masato Nomura

  NATURAL PRODUCT RESEARCH TAYLOR & FRANCIS LTD 28 (3) 201 - 204 1478-6419 2014/02 [Refereed]
   

  The methanol extract of Coreopsis lanceolata L. petals was acid-hydrolysed, and 7,3,4-trihydroxy-8-methoxyflavanone (1) and 6,3,4-trihydroxy-7-methoxyaurone (leptosidin) (2) were successfully isolated. The structure of compound 1 is designated to flavanone based on X-ray crystallographic analysis and NMR spectroscopic analysis. Compound 1 showed high-antioxidant effects based on diphenylpicrylhydrazyl radical scavenging assay (94.3% scavenging rate) and superoxide dismutase-like activity assay (23.9% inhibition rate).
• CONVENIENT SYNTHESIS OF 1-(TRIMETHYLSILYL)- AND 1-(TRIMETHYLSTANNYL)VINYLPHOSPHONATES

  Yoshiharu Okada; Tomohiro Maruyama; Shin-ichi Tamura; Hirohito Kameoka; Satoshi Masuda; Yuichiro Tokuda; Junya Sakai; Masato Nomura

  PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS TAYLOR & FRANCIS LTD 189 (6) 778 - 790 1042-6507 2014 [Refereed]
   

  Dimethyl 1,1-bis(trimethylsilyl)methylphosphonate and dimethyl 1-(trimethylsilyl)-1-(trimethylstannyl)methylphosphonate were succeeded to react with aromatic aldehydes in the presence of methyl benzoate as additive to give the corresponding vinylphosphonates in moderate yields.
• A Study on Fatty Acids in Seeds of Euterpe oleracea Mart Seeds

  Yoshiharu Okada; Tomoyuki Motoya; Shinichi Tanimoto; Masato Nomura

  JOURNAL OF OLEO SCIENCE JAPAN OIL CHEMISTS SOC 60 (9) 463 - 467 1345-8957 2011/09 [Refereed]
   

  Fatty acids of Euterpe oleracea Mart seeds were analyzed in hexane and diethyl ether extracts. The hexane extract contained dodecanoic acid (3), tetradecanoic acid (4), hexadecanoic acid (7), and 9-octadecenoic acid (10). The diethyl ether extract contained (10). The oil of Mart seeds was obtained firstly by methanol extract and further extracted with diethyl ether. The hexane and diethyl ether extracts were then analyzed for antioxidant effects. Both extracts demonstrated a 1,1-diphenyl-2-picrylhydrazyl radical elimination effect similar to that of alpha-tocopherol and an active oxygen inhibition effect. Significant quantities (0.6212 mg/mL) of poly phenol, in comparison to the standard rejected gallic acid, were found in the extract oil of Mart seeds by the methanol extraction.
• Effect of impregnation using sucrose solution on stability of anthocyanin in strawberry jam

  Yoshiyuki Watanabe; Kazunori Yoshimoto; Yoshiharu Okada; Masato Nomura

  LWT-FOOD SCIENCE AND TECHNOLOGY ELSEVIER SCIENCE BV 44 (4) 891 - 895 0023-6438 2011/05 [Refereed]
   

  Strawberry impregnated with sucrose was used for the jam preparation, and its effects on the stability of anthocyanins and the jam color were examined. The amount of sucrose in impregnated strawberry depended on the concentration of sucrose solution and the operation time for the impregnation. In comparison with only the addition of sucrose to the jam preparation, the impregnation of strawberry in advance of the jam preparation stabilized anthocyanins in the jam. The antioxidative ability of the strawberry jam correlated with the amount of anthocyanin. Furthermore, the rate constants by the Weibull model for the degradation of anthocyanins and the chromatic deterioration of the jam were estimated, and the relationship between the two rate constants was found to be almost linear. It was shown that the impregnation of strawberry with sucrose was effective for improving functions, such as antioxidative activity and the color of its jam. (C) 2010 Elsevier Ltd. All rights reserved.
• Pharmacological Activity of Compounds Extracted from Persimmon Peel (Diospyros kaki THUNB.)

  Satomi Fukai; Shinichi Tanimoto; Aki Maeda; Hitomi Fukuda; Yoshiharu Okada; Masato Nomura

  JOURNAL OF OLEO SCIENCE JAPAN OIL CHEMISTS SOC 58 (4) 213 - 219 1345-8957 2009/04 [Refereed]
   

  Persimmon peels (Diospyros kaki THUNB.) are discarded during the production of dried fruit. The 2-methoxy-4-vinyl phenol (8) which is component of persimmon peel had high antioxidant activity on the DPPR (1,1-diphenyl-2-picrylhydrazyl) radical scavenging assay and SOD (superoxide dismutase) assay. And (8) had higher tyrosinase inhibiting activity than that of arbutin using both L-tyrosine and L-DOPA as substrates. In addition, tyrosinase inhibiting activity of synthesized 2-methoxy-4-vinylphenol glycoside (8a) was studied. (8a) had tyrosinase inhibiting activity, suggesting that (8a) has possibilities for ingredient of cosmetics that are possessed of whitening effect.
• Chemical Constituents of Coreopsis lanceolata L. and Their Physiological Activities

  Shinichi Tanimoto; Mitsuo Miyazawa; Toshio Inoue; Yoshiharu Okada; Masato Nomura

  JOURNAL OF OLEO SCIENCE JAPAN OIL CHEMISTS SOC 58 (3) 141 - 146 1345-8957 2009/03 [Refereed]
   

  Petals from Coreopsis lanceolata L. were extracted in methanol and subjected to solvent-solvent partitioning to yield four fractions: hexane, diethyl ether, ethyl acetate, and aqueous. These fractions were screened using a 1,1-diphenyl-2-picrylhydrazyl radical scavenging assay and an active oxygen inhibition assay. The ethyl acetate extract contained the highest level of active components. Four compounds isolated from this fraction by HPLC were screened for antioxidant activity and anti-allergic activity. Anti-allergic activity was assessed by measuring release of histamine from rat peritoneal mast cells. One compound, termed laceolin, was characterized by spectroscopic analysis, including extensive NMR and mass spectra. This compound had significant radical scavenging activity, with an SC50 (scavenging concentration of 50%) value of 2.6 mu g/mL and superoxide dismutase activity of 46.2%.
• Synthesis and cosmetic whitening effect of glycosides derived from several phenylpropanoids

  Shinichi Tanimoto; Hitoshi Tominaga; Yoshiharu Okada; Masato Nomura

  Yakugaku Zasshi 126 (3) 173 - 177 0031-6903 2006/03 [Refereed]
   

  Plant-derived phenylpropanoid compounds (4-ethyl-2-methoxyphenol, 2,6-dimethoxyphenol, 2,3-dimethoxyphenol, 3,4-dimethoxyphenol, 3,5-dimethoxyphenol, 3,4-dihydroxycinnamic acid, 4-hydroxy-3-methoxycinnamic acid, and 3-hydroxy-4-methoxycinnamic acid) were glycosidated to form glycoside compounds. We evaluated the effects of these compounds on the inhibition of tyrosinase and melanin synthesis and their cytotoxicity from the viewpoint of their use as whitening agents in cosmetics. Some compounds had more potent tyrosinase-inhibiting activity than commercial arbutin, which was used as a control, and showed no cytotoxicity at low concentration ranges. © 2006 The Pharmaceutical Society of Japan.
• Synthesis and Physiological Activities of Monoterpene Carboxylic Acid Esters with Pyrones

  Shinya Tachibana; Yuki Ohno; Yoshihito Fujihara; Yoshiharu Okada; Masaaki Sugiura; Shigeki Takagi; Masato Nomura

  Journal of Oleo Science 55 (4) 181 - 189 1347-3352 2006 [Refereed]
   

  We are conducting research into the synthesis of bioactive substances that are based on monoterpenoids. As part of this research, here we synthesized a compound that introduced three kinds of pyrones (a)-(c) (which are used for flavor and are known to be problem-free from a safety aspect) into the lateral chain of four types of monoterpenoids (1)-(4), and examined which of these compounds manifest miticidal activities. The results show that, of the functional groups introduced into the lateral chain, the miticidal effect of 4-hydroxy-6-methyl-2-pyrone was especially good. Of the compounds synthesized here, it was possible to clarify that compounds (1b) and (3b) showed miticidal activity. © 2006, Japan Oil Chemists' Society. All rights reserved.
• Synthesis of phosphine oxide-carboxylic acid esters bearing 9,10-dihydro-9,10-ethanoanthracene moiety

  Y Okada; K Okeya; Y Murata; N Aoki; T Aoki; M Sugitani; S Yasui; Y Sawada; F Ogura

  PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS TAYLOR & FRANCIS LTD 178 (4) 821 - 829 1042-6507 2003/04 [Refereed]
   

  A bulky type. of phosphine oxide-carboxylic acid bearing 9,10-dihydro-9,10-ethanoanthracene moiety was synthesized by the Diels-Alder reaction of 2-anthryldiphenylphosphine oxide and methyl acrylate, for which the structure was confirmed on the basis of H-1 NMR spectral data to be dimethyl 2-diphenylphosphinoyl-9,10-dihydro-9,10-ethanoanthracene-11,11- and 12,12-dicarboxylates.
• Synthesis of chiral 3-(o-diphenylphosphinophenyl)-butanoic acid and its palladium complex catalyzed asymmetric allylic alkylation

  Y Okada; Y Murata; D Une; Sasanuma, I; F Ogura

  PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS TAYLOR & FRANCIS LTD 177 (8-9) 1973 - 1974 1042-6507 2002/08 [Refereed]
  
• DEVELOPMENT OF CHIRAL PHOSPHINE-LIGANDS BEARING A CARBOXYL GROUP AND THEIR APPLICATION TO CATALYTIC ASYMMETRIC REACTION

  T MINAMI; Y OKADA; T OTAGURO; S TAWARAYA; T FURUICHI; T OKAUCHI

  TETRAHEDRON-ASYMMETRY PERGAMON-ELSEVIER SCIENCE LTD 6 (10) 2469 - 2474 0957-4166 1995/10 [Refereed]
   

  A new chiral phosphine ligand bearing a carboxyl group, 3-(diphenylphosphino)butanoic acid, was developed and used for palladium catalyzed asymmetric allylic alkylation of cyclic cis-allylic acetates such as 2-cyclopentenyl, 2-cyclohexenyl, and 2-cycloheptenyl acetate. These acetates reacted with triethyl sodiophosphonoacetate in the presence of the palladium catalyst with the ligand to give the corresponding alkylation products in good enantiomeric excesses.
• CONSTRUCTION OF ALPHA-PHOSPHONOLACTAMS VIA RHODIUM (II)-CATALYZED INTRAMOLECULAR C-H INSERTION REACTIONS

  Y OKADA; T MINAMI; M MIYAMOTO; T OTAGURO; S SAWASAKI; J ICHIKAWA

  HETEROATOM CHEMISTRY VCH PUBLISHERS INC 6 (3) 195 - 210 1042-7163 1995/05 [Refereed]
   

  The Rh(II)-catalyzed intramolecular C-H insertion reactions of N,N-dialkyl-alpha-diazo-alpha-(diethylphosphone)acetamides 2a,f-j in CHCl3 or ClCH2CH2Cl were found to give monocyclic and bicyclic alpha-phpsphono-beta-lactams, 3a and 3f-j, in 43-67% yields via regiospecific alpha-C-H insertion of the N-alkyl groups. Similar treatment of N-benzyl-N-isopropyl-alpha-diazo-alpha-(diethylphosphono)acetamide (2b) and the corresponding N-isobutyl-N-methylacetamide 2d in ClCH2CH2Cl afforded mixtures of beta-lactams 3b (35%) and 3b' (16%), beta-lactam 3d (47%), and gamma-lactam 4d (10%), respectively, each of which is formed by the competitive C-H insertion reaction between benzylic and isopropyl alpha-C-H bonds and between methyl alpha-C-H and methine beta-C-H bonds, respectively. For the formation of beta-lactams, the selectivity in the rhodium-mediated C-H insertion in ClCH2CH2Cl follows the order methyl > methine > benzylic alpha-C-H bond on N-substituents. The N,N-dibutyl-alpha-diazo homologue 2c and N-[alpha-diazo-alpha-(diethylphosphono)acetyl]-2-methylindoline (2k) exclusively produced gamma-lactams 4c (67%) and 4k (81%) via insertion into the methylene beta-C-H and methyl beta-C-H bonds. tert-Butyl N-[alpha-diazo-alpha-(dibenzylphosphone)acetyl]-piperidine-2-carboxylate (2m) on similar treatment, followed by deprotection of the benzyl ester afforded the 7-phosphono carbacepham 6 in 32% overall yield. Similar Rh(II)-catalyzed cyclization of N-methyl-N[4-benzyloxy-alpha-(diethylphosphono)-phenyl(diethyl-phosphono)methyl]-alpha-diazo-acetamide (2n) led to 1-[4'-benzylphenyl(diethylphosphono)methyl]--3-(diethyl-phosphono)azetidin-2-one (3n) in 78% yield. The phosphono group at C-7 of 3f was converted into the acetylamino group via a four-step reaction. Application of chiral rhodium(II) carboxylates 12a-c to the insertion reactions of 2b,c produced alpha-phosphono-beta- and gamma-lactams, 3b and 4c, in 6-24% ee and 25-29% ee, respectively.
• INTRAMOLECULAR ENE REACTION OF VINYLPHOSPHONATES - SYNTHETIC APPLICATION TO BICYCLIC COMPOUNDS AND CADALANE AND VALERENIC ACID TERPENOIDS

  T MINAMI; T UTSUNOMIYA; S NAKAMURA; M OKUBO; N KITAMURA; Y OKADA; J ICHIKAWA

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 59 (22) 6717 - 6727 0022-3263 1994/11 [Refereed]
   

  The Lewis-acid-catalyzed intramolecular ene-reaction of vinylphosphonates 4, 6, and 7, prepared by the Knoevenagel condensation of triethyl phosphonoacetate (3) with citronellal (1) or 2,6-dimethyl-5-heptenal(2), stereoselectively gave 2-(8'-p-menthen-3'-yl) or 2-(2'-isopropenyl-5'-methylcyclopent-1'-yl)phosphonoacetates 8-10 in high yields. The Wittig-Horner reaction of the phosphonates 8-10 with paraformaldehyde led to 1,5-diene compounds 12a,b and 13b in 87-90% yield. Subsequent Lewis-acid-catalyzed cyclization of the compounds 12, 13 or 25, 27 afforded 1,6-dimethyloctahydronaphthalene-4-carboxylates 17, 22, or carbaldehydes 28, 29 and/or 8-methyl-2,5-dimethylenebicyclo[4.4.0]decan-4-ol (30). Palladium-catalyzed metallo-ene reaction of the acetate 32 afforded 2,5,8-trimethyl-1,2,3,4-tetrahydronaphthalene (34). The bicyclic compounds 17a and 29 were applied to the synthesis of cadalane and valerenic acid sesquiterpenoids.
• COPPER(I) SALT-MEDIATED ARYLATION OF PHOSPHINYL-STABILIZED CARBANIONS AND SYNTHETIC APPLICATION TO HETEROCYCLIC-COMPOUNDS

  T MINAMI; T ISONAKA; Y OKADA; J ICHIKAWA

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 58 (25) 7009 - 7015 0022-3263 1993/12 [Refereed]
   

  The copper-mediated reaction of phosphinyl-stabilized carbanions 2a-c with aryl halides 1a-i in DMF or HMPA produced (arylmethyl)phosphonates 3-11 in good yields. Similar treatment of N-(2-iodophenyl)- and N-(2-iodophenyl)-N-methyl-alpha-(diethoxyphosphinyl)acetamides (12 and 14) led to 2-[(diethoxyphosphinyl)methyl]benzoxazole (13) and 1-methyl-3-(diethoxyphosphinyl)oxindole (15) in 71 and 85% yields, respectively. 4-(Ethoxycarbonyl)-3,4-dihydroisoquinoline N-oxide (33) was synthesized by the reaction of ethyl alpha-(o-formylphenyl)acrylate (31), derived from 6 and paraformaldehyde,with hydroxylamine. The cycloaddition of 33 to olefins such as dimethyl maleate, methyl acrylate, and styrene was studied.
• A Novel Type of Chiral Diphosphine Ligand, trans-2,3-Bis(diphenylphosphino)-1-methyl-1-cyclopropanecarboxylic Acid and Asymmetric Allyic Alkylation by the Use of Its Palladium Complex (共著)

  Y. Okada; T.Minami; J. Ichikawa

  Phosphorus, Sulfur, and Silicon, and the Related Elements 77 153  1993 [Refereed]
  
• A NOVEL TYPE OF CHIRAL DIPHOSPHINE LIGAND, TRANS-2,3-BIS(DIPHENYLPHOSPHINO)-1-METHYL-1-CYCLOPROPANECARBOXYLIC ACID AND ASYMMETRIC ALLYLIC ALKYLATION BY THE USE OF ITS PALLADIUM COMPLEX

  Y OKADA; T MINAMI; T YAMAMOTO; J ICHIKAWA

  CHEMISTRY LETTERS CHEMICAL SOC JAPAN 1992 (4), 547-550 (4) 547 - 550 0366-7022 1992/04 [Refereed]
   

  Optically active trans-2,3-bis(diphenylphosphino)-1-methyl-1-cyclopropanecarboxylic acid was synthesized from trans-1,2-bis(diphenylphosphinyl)ethene via resolution of the racemic diphosphine oxide. Asymmetric allylic alkylation of 2-cyclohexenyl acetate with l-menthyl sodiodiethylphosphonoacetate was achieved in good optical yields by the use of its palladium complex.
• SYNTHESIS OF A NOVEL TYPE OF CHIRAL PHOSPHINOCARBOXYLIC ACIDS - THE PHOSPHINE-PALLADIUM COMPLEXES CATALYZED ASYMMETRIC ALLYLIC ALKYLATION

  Y OKADA; T MINAMI; Y UMEZU; S NISHIKAWA; R MORI; Y NAKAYAMA

  TETRAHEDRON-ASYMMETRY PERGAMON-ELSEVIER SCIENCE LTD 2 (7) 667 - 682 0957-4166 1991 [Refereed]
   

  A novel type of chiral cycloalkylphosphines bearing the carboxy group at the beta-position were developed, and used for palladium catalyzed asymmetric alkylation of allylic substrates such as 2-cyclohexenylacetate and 1,3-disubstituted-propenyl acetates (R1CH = CHCH(OAc)R2: R1 = R2 = Ph; R1 = Ph, R2 = (CH2)4OAc; R1 = Ph, R2 = (CH2)6OAc; R1 = Ph, R2 = (CH2)10OAc). Reaction of the propenyl acetates with soft carbon nucleophiles such as triethyl sodiophosphonoacetate and sodiomalonic acid esters in the presence of a palladium catalyst prepared in situ from Pd(OAc)2 and chiral (2-diphenylphosphino)cycloalkanecarboxylic acids (7a,b) gave high yields of alkylation products (PhCH = CHCH(X)Ph: > 77 %ee for X = CH(CO2Et)P(O)(OEt)2 and > 72 %ee for X = CH(CO2Me)2). The alkylation products 15 and 28a-c were converted into optically active alpha-methylene-gamma-lactone and alpha-methylene macrolide derivatives. The high stereoselectivity demonstrated by the chiral phosphinocarboxylic acid-palladium catalyzed allylic alkylation suggested to be caused by an electronic repulsion between the carboxy group on the ligand and the incoming soft carbon nucleophile, which directs the nucleophilic attack on one of the pi-allyl carbons.
• THE 1ST SYNTHESIS OF CHIRAL PHOSPHINOCARBOXYLIC ACID LIGANDS, TRANS-2-(DIPHENYLPHOSPHINO)CYCLOALKANECARBOXYLIC ACIDS - THE PHOSPHINE-PALLADIUM COMPLEXES CATALYZED ASYMMETRIC ALLYLIC ALKYLATION

  Y OKADA; T MINAMI; Y SASAKI; Y UMEZU; M YAMAGUCHI

  TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 31 (27) 3905 - 3908 0040-4039 1990 [Refereed]
  
• SYNTHESIS AND REACTION OF (3-PHENYLSELENO-1-ALKENYL)TRIPHENYLPHOSPHONIUM SALTS

  T MINAMI; M NAKAYAMA; T NAKAMURA; Y OKADA

  CHEMISTRY LETTERS CHEMICAL SOC JAPAN 1989 (10), 1741-1742 (10) 1741 - 1742 0366-7022 1989/10 [Refereed]
  
• NEW SYNTHESIS OF CYCLOBUTANE ANNELATED COMPOUNDS BY THE USE OF A (1-CYCLOBUTENYL)TRIPHENYLPHOSPHONIUM SALT

  Y OKADA; T MINAMI; S YAHIRO; K AKINAGA

  JOURNAL OF ORGANIC CHEMISTRY AMER CHEMICAL SOC 54 (4) 974 - 977 0022-3263 1989/02 [Refereed]
  
• [Cycloalkyl(phenylseleno)methylene]triphenylphosphoranes: Synthesis and reactions of (phenylseleno)alkenes

  T. Minami; Y. Umezu; S. Shikita; Y. Okada

  Bulletin of the Chemical Society of Japan 62 (11) 3724 - 3726 0009-2673 1989 [Refereed]
  
• Synthesis and Reactions of (2-OxocyctobutyI)diphenyIphosphine Oxide

  Yoshiharu Okada; Toru Minami; Shigenori Yahiro; Hideki Kaku; Munetaka Ishiyama

  Nippon Kagaku Kaishi 1987 (7) 1244 - 1249 0369-4577 1987 [Refereed]
   

  We succeeded in the synthesis of (2-oxocyclobutyl)diphenylphosphine oxide [4] (1-cyclobutenyl)triphenylphosphoniuim salt [1] in good yield. Reaction of [4] with methanol gave methyl 4-(diphenylphosphinyl)butyrate [5] in 64% yield. Reaction of [4] with Schiff bases such as N-isobutylidenebenzylamine [6a], N-benzylidenebutylamine [6 b], and N-benzylideneisopropylamine (6 c] gave N-benzyl-5-Cdiphenylphosphinyl-6-isopropyl-2-pipe-ridinone [7a] (28%), 4-(diphenylphosphinyl)-4-pentenamides [8 a-c] (33~44%), and 4-(diphenylphosphinyl)butyramides [9 a, c] (24~32%), respectively. Reaction of [4] with diazomethane gave the ring-expansion products, (2-oxocyciopentyl)diphenylphosphine oxide [10] (39~61%) and (2-methoxy-l-cyclopentenyl)diphenylphosphine oxide [11] (6~40%). Reaction of the enolate anion of the cyclobutanone [4] with diphenyl phosphorochloridate and benzoyl chloride produced enol esters of the cyclobutanone, [13] and [14] respectively, in good yields. Reaction of enol diphenylphosphate ester [13] with lithium dibutyleuprate (I) gave (2-butyl-l-cyclobutenyl)diphenylphosphine oxide [15] in 32% yield. The Diels-Alder reactions of 3-substituted 2-diphenylphosphmyl~l, 3-butadienes, generated by thermolysis of (2-substituted l-cyclobutenyl)diphenylphosphine oxides [14] and [15] with N-phenyl-maleimide gave functionalized (l-cyclohexenyl)diphenylphosphine oxides [16] (28%) and [17] (82%). Reaction of [4] with benzaldehyde did not give the Wittig-Horner reaction product, but 4-(diphenylphosphinyl)-5-phenyl-4-pentenoic acid [20] was obtained in 53% yield. © 1987, The Chemical Society of Japan. All rights reserved.
• SYNTHESIS AND RESOLUTION OF A NEW TYPE OF CHIRAL BISPHOSPHINE LIGAND, TRANS-BIS-1,2-(DIPHENYLPHOSPHINO)CYCLOBUTANE, AND ASYMMETRIC HYDROGENATION USING ITS RHODIUM COMPLEX

  T MINAMI; Y OKADA; R NOMURA; S HIROTA; Y NAGAHARA; K FUKUYAMA

  CHEMISTRY LETTERS CHEMICAL SOC JAPAN 1986 (4), 613-616 (4) 613 - 616 0366-7022 1986/04 [Refereed]
  

Books etc

• リンの辞典

  岡田 芳治 (Contributor農薬)朝倉書店 2017/11

Conference Activities & Talks

• Canadensolideの合成研究  [Not invited]

  流出未那; 岡田芳治

  日本化学会第103春季年会  2023/03
• Brachydin類の合成研究  [Not invited]

  森田麻祐子; 岡田芳治

  日本化学会第103春季年会  2023/03
• 天然物を指向したビニルシランの調製と利用  [Not invited]

  森田麻祐子; 岡田芳治

  第49回有機典型元素化学討論会  2022/12
• β-ケトホスホナートの5員環含有天然物合成への応用  [Not invited]

  大塚彩加; 森田麻祐子; 岡田芳治

  第49回有機典型元素化学討論会  2022/12
• ホスフィンカルボン酸配位子の合成と利用  [Not invited]

  走出航介; 岡田芳治

  2022年日本化学会中国四国支部大会 広島大会  2022/11
• Brachydin類の合成研究  [Not invited]

  森田麻祐子; 岡田芳治

  第12回CSJ化学フェスタ2022  2022/10
• Brachydin BおよびCの合成研究  [Not invited]

  森田麻祐子; 岡田芳治

  日本化学会第102春季年会  2022/03
• ブチロラクトン型リグナンの合成研究  [Not invited]

  大塚彩加; 岡田芳治

  日本化学会第102春季年会  2022/03
• ブチロラクトン型リグナンの合成研究  [Not invited]

  大塚 彩加; 岡田 芳治

  ２０２１年日本化学会中国四国支部大会 高知大会  2021/11
• 分子内C–H結合挿入反応を利用したジャスモン酸類の合成研究  [Not invited]

  森田 麻祐子; 岡田 芳治

  ２０２１年日本化学会中国四国支部大会 高知大会  2021/11
• Brachydin Bの合成研究  [Not invited]

  森田 麻祐子; 岡田 芳治

  第11回CSJ化学フェスタ2021  2021/10
• Acerogenin類の簡単合成と生理活性  [Not invited]

  大畠伊久美; 流出未那; 岡田芳治

  日本化学会第101春季年会  2021/03
• 分子内C-H結合挿入反応を利用したジャスモン酸類の合成研究  [Not invited]

  森田麻祐子; 岡田芳治

  日本化学会第101春季年会  2021/03
• Synthesis of Brachydin B and Its Analogues  [Not invited]

  Ami Sasajima; Yoshiharu Okada

  日本化学会第100春季年会  2020/03
• Brachydin Bの合成研究（２）

  笹島杏実; 岡田芳治

  日本化学会中国四国支部大会徳島大会  2019/11
• Synthesis of Brachydin B and Its Analogues  [Not invited]

  YAMAMOTO Takaya; SASAJIMA Ami; OKADA Yoshiharu

  日本化学会第99春季年会  2019/03
• β-置換ビニルシランの簡便合成とその合成化学的利用  [Not invited]

  山本 貴也; 井川 雅貴; 岡田 芳治

  日本化学会第98春季年会  2018/03
• フラボノイド類の生理活性について  [Not invited]

  岡田芳治; 中坊大輔; 野村正人

  日本化学会第97春季年会  2017/03
• α位にシリル基を有するビニルホスホナートの合成化学的利用  [Not invited]

  服部拓哉; 岡田芳治; 野村正人

  日本化学会第97春季年会  2017/03
• α-ホスホノアゼチジノンの不斉合成  [Not invited]

  岡田芳治; 松葉千帆; 野村正人

  日本化学会第97春季年会  2017/03
• 新規ホスフィンカルボン酸配位子の合成と不斉合成への応用  [Not invited]

  岡田芳治; 髙木裕太

  日本化学会第97春季年会  2017/03
• アセロゲニン類の簡単合成と生理活性  [Not invited]

  岡村麻由; 大塚結加; 藤原まゆか; 渡邉紗代; 岡田芳治

  日本化学会第97春季年会  2017/03
• Simple Synthesis and Physiological Activities of Acerogenins  [Not invited]

  Mayu Okamura; Masato Nakamoto; Yoshiharu Okada

  17th Tetrahedron Symposium  2016/06
• Isolation of Flavonoids in Coreopsis lanceolata L. Petals and Their Synthesis with β-Ketophosphonates  [Not invited]

  岡田 芳治; 佐多平 泰成; 賀美 誠也; 岡野 友香; 野村 正人

  日本化学会第９３春季年会  2013/03  草津  日本化学会第９３春季年会
   

  乾燥したオオキンケイギク花弁中から7,3',4'-トリヒドロキシ-8-メトキシフラバノンの単離に成功した。この化合物は高い抗酸化活性を有していた。ピロガロールを出発物質にα-ジメチルホスホノ‐2-ヒドロキシアセトフェノン類を調製した。THF溶媒中DBUなどの有機塩基存在下、各種アルデヒドと反応させ、対応するカルコン誘導体を合成した後、フラバノン誘導体への変換を検討した。
• 多官能化されたメチルホスホナートの合成化学的利用（４）  [Not invited]

  岡田 芳治; 田村 真一; 増田 智司; 徳田 雄一郎; 野村 正人

  日本化学会  2012  第91春季年会（横浜）  日本化学会
  
• 多官能化されたメチルホスホナートの合成化学的利用  [Not invited]

  岡田 芳治; 田村 真一; 増田 智司; 徳田 雄一郎; 野村 正人

  日本化学会  2011/11  ２０１１年日本化学会西日本大会（徳島）  日本化学会
  
• オオキンケイギク花弁中の生理活性物質について  [Not invited]

  沖田 真理; 谷本 真一; 岡田 芳治; 野村 正人

  日本化学会  2011/11  ２０１１年日本化学会西日本大会（徳島）  日本化学会
  
• 2,3-ビスジエチルホスホノ-1,3-ブタジエンの合成化学的利用  [Not invited]

  岡田 芳治; 野村 正人; 加藤 隆一

  日本化学会  2011/11  ２０１１年日本化学会西日本大会（徳島）  日本化学会
  
• 2,3-ビスジエチルホスホノ-1,3-ブタジエンの合成化学的利用(3)  [Not invited]

  岡田 芳治

  日本化学会第91春季年会  2011/03  神奈川  日本化学会第91春季年会
  
• 天然物を指向したb-ケトホスホナートの合成化学的利用(4)  [Not invited]

  岡田 芳治

  日本化学会第91春季年会  2011/03  神奈川  日本化学会第91春季年会
  
• 天然物を指向したβ-ケトホスホナートの合成化学的利用（３）  [Not invited]

  岡田 芳治

  日本化学会  2010/03  第90春季年会（東大阪）  日本化学会
  
• 多官能化されたメチルホスホナートの合成化学的利用（３）  [Not invited]

  岡田 芳治

  日本化学会  2010/03  第90春季年会（東大阪）  日本化学会
  
• モノテルペン配位子の合成と利用  [Not invited]

  岡田 芳治

  日本化学会  2010/03  第90春季年会（東大阪）  日本化学会
  
• 天然物を指向したβ-ケトホスホナートの合成化学的利用  [Not invited]

  岡田 芳治

  日本化学会  2009/11  ２００９年日本化学会西日本大会（松山）  日本化学会
  
• 多官能化されたメチルホスホナートの合成化学的利用  [Not invited]

  岡田 芳治

  日本化学会  2009/11  ２００９年日本化学会西日本大会（松山）  日本化学会
  
• Convenient Synthesis of 3-(Dialkylphosphono)chroman-2- and 4-ones  [Not invited]

  岡田 芳治

  IUPAC  2009/08  42nd IUPAC Congress(Glasgow)  IUPAC
  
• リン官能基を有するフェニルプロパノイド誘導体の簡便合成  [Not invited]

  岡田 芳治

  日本化学会  2009/03  第89春季年会（船橋）  日本化学会
  
• 天然物を指向したβ-ケトホスホナートの合成化学的利用  [Not invited]

  岡田 芳治

  日本化学会  2009/03  第89春季年会（船橋）  日本化学会
  
• 多官能化されたメチルホスホナートの合成化学的利用（２）  [Not invited]

  岡田 芳治

  日本化学会  2009/03  第89春季年会（船橋）  日本化学会
  
• モノテルペン配位子の合成と利用  [Not invited]

  岡田 芳治

  日本化学会  2009/03  第89春季年会（船橋）  日本化学会
  
• 実験，実習をベースとした生物工学/化学の導入・動機づけ教育への取り組み－平成15年度文部科学省サイエンス・パートナーシップ・プログラム報告－  [Not invited]

  白石 浩平; 鈴木 克之; 仲宗根 薫; 岡田 芳治

  平成17年度（第53回）日本工学教育協会  2005/09  広島  平成17年度（第53回）日本工学教育協会
   

  平成15年度文部科学省サイエンス・パートナーシッププログラム採択事業についての研究成果を報告した。 動機付け教育として実験、実習が効果的であり、生徒・学生の学習活動が継続的に行なわれれば、自学自習によって高度な教育が可能であることが示唆された。同時に実験・実習内容の精査やプログラム以前での実験技術に拘わる事前実習やティーティングアシスタントの養成が重要であることを指摘した。

MISC

• MagnololおよびHonokiol配糖体の美肌効果に関する研究

  澤邊 昭義; 山下 敦之; 竹田 竜嗣; 井上 俊夫; 石井 まや; 谷本 真一; 横野 一歩; 岡田 芳治; 野村 正人  日本栄養・食糧学会大会講演要旨集  71回-  357  -357  2017/04
• Studies on Cosmetic Whitening Effect and Antibacterial Activities of Dry Persimmon Peel (Diospyros Kaki THUNB.)

  OKADA Yoshiharu; FUKAI Satomi; OTSUBO Eiji; NOMURA Masato  近畿大学工学部研究報告  (45)  7  -15  2011
• Chemical constituents of YUZU and LIME essential oils and their antioxidative activities

  Shinya Tachibana; Shinichi Tanimoto; Yoshihira Murai; Yoshiyuki Watanabe; Yoshiharu Okada; Masato Nomura  近畿大学次世代基盤技術研究所報告  2-  45  -51  2011
• 1.Synthesis and Physiological Activity of Ureas and Amides Derived from Aminoadamantanes

  TANIMOTO Shinichi; KITAZAWA Toshihiro; OKADA Yoshiharu; NOMURA Masato  Research reports of the Faculty of Engineering, Kinki University  41-  1  -9  2007
• Skin Protection Effect of Heterocyclic Compounds Synthesized from Trans-Anethole Derivatives

  KOIKE Takashi; TANIMOTO Shinichi; OKADA Yoshiharu; FUKUDA Hitomi; KOBAYASHI Yuka; MORIGAKI Eiji; TOMINAGA Hitoshi; MATSUYAMA Hideki; NOMURA Masato  Research reports of the Faculty of Engineering, Kinki University  40-  1  -7  2006/12
• ラクトン環、ラクタム環を有する生物活性関連化合物の触媒的不斉合成（研究課題番号：16550103) 平成16年度～17年度科学研究費補助金（基盤研究 (C)）研究成果報告書

  岡田 芳治  2006/03
• Synthesis and Physiological Activity of Urea and Amide Compounds with an Optically Active Isopinocamphenyl Moiety

  KITAZAWA Toshihiro; FUKUDA Hitomi; OKADA Yoshiharu; FUJIHARA Yoshihito; SUGIURA Masaaki; TAKAGI Shigeki; NOMURA Masato  Research reports of the Faculty of Engineering, Kinki University  39-  1  -9  2005/12
• マスタリング･バイオ／化学実験（化学実験を体験、基本操作をマスターしよう）（採択番号：連39) 平成16年度文部科学省サイエンス・パートナーシップ・プログラム（SPP）実施報告書

  岡田 芳治  2005/03
• Synthesis of a Novel Type of a-Phosphonocyclobutanones Using Rh(II)-Catalyzed C-H Insertion Reaction

  OKADA Yoshiharu; KITA Kazuyo; KOTAKI Masanori; HANE Yukiko; OGURA Fumio  Research reports of the School of Engineering, Kinki University  37-  49  -52  2003/12
• Miticidal Activity of Monoterpenyl Carboxypyrrolidinamides and Piperidinamides

  Kazuo Kasemura; Shinji Fujita; Yoshiharu Okada; Yoshihito Fujihara; Masato Nomura  Journal of Oleo Science  52-  (1)  41  -46  2003  [Refereed]
  
• Skin Whitening Effects of Estragole Derivatives

  Yutaka Motoki; Shinji Fujita; Yoshihito Fujihara; Yoshiharu Okada; Masato Nomura  Journal of Oleo Science  52-  (9)  495  -498  2003  [Refereed]
  

Research Grants & Projects

• Catalytic Asymmetric Synthesis of Physiologically Active Related compounds Bearing Lactone or Lactam Ring

  Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research

  Date (from‐to) : 2004 -2005 

  Author : OKADA Yoshiharu; NOMURA Masato

   

  In the transition metal complex catalyzed asymmetric synthesis, one of the most important needs is the development of effective chiral ligands. We describe here the synthesis of a bulky type of 2-diphenylphosphino-9,10-dihydro-9,10-ethanoanthracene bearing carboxyl group. Reaction of 1 with methyl acrylate gave an isomer mixture of 2a-d in 94% yield. Recrystallization of the mixture from ethyl acetate-hexane gave a pure 2b as a first crystal. Recycling preparative HPLC of the filtrate with CHCl_3 was succeeded to separate 2a. Reduction of 2b with HSiCl_3 and subsequent alkaline hydrolysis gave (±)-2-diphenylphosphino-9,10-dihydro-9,10-ethanoanthracene-12(anti)-carboxylic acid (3b) in 43% yield. Resolution of (±)-3b with (-)-α-methylbenzyl-amine was succeeded to give an optically pure (-)-3b, [α]_D^<23>=-37.55 (c 0.39, CHCl_3). The reaction of triethyl sodiophosphonoacetate with 2-cyclohexenyl acetate in the presence of Pd(OAc)_2・(-)-3b (1.5 mol%) gave the allylic alkylation product in 96% (53%ee). On the other hand, many compounds containing thiazolidinedione moiety such as rosiglitazone and pioglitazone have been useful as the medicine. However, the convenient synthesis of thiazolidine derivatives having phosphorus functional group has been rarely reported, to our knowledge. We now report the synthesis and synthetic application of 5-(diethylphosphono)-1,3-thiazolidine derivatives. Treatment of triethyl phosphonoacetate with sodium hydride and powdered sulfur generated thiolate anion intermediate. And subsequent reaction with phenyl isocyanate (4a) gave thiocarbamate 5a in 40% yield. While similar reaction with benzyl isocyanate (4b) gave 3-benzyl-5-(diethylphosphono)-1,3-thiazolidinedione (6b) in 8% yield together with thiocarbamate 5b in 25% yield.
• SYNTHESES OF NEW ORGANIC ELECTRON DONORS, ACCEPTORS, AND THEIR CHARGE-TRANSFER COMPLEXES, AND STUDIES ON THEIR PROPERTIES

  Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research

  Date (from‐to) : 1999 -2000 

  Author : OGURA Fumio; OKADA Yoshiharu

   

  The target molecules of this research projects are novel organic electron donors (1) and acceptors (2,3,4), which are expected to act as effective components to form charge-transfer complexes exhibiting high electric conductivities. The molecule, 1, carries two 7π electron rings fused to a naphthalenene at its two peri-positions and is expected to behave as a good electron donor in the two stage redox processes. Synthesis of 1 is started from acenaphthene. It was transformed to 1,8-Bis (dibromomethyl)-4,5-dichloronaphthalene by 5 reaction steps. The dibromide was reacted with cis-4,5-bis (boryl) octene, prepared from bis [pinacolato] diboron and 4-octyne, to yield a pleiadene derivative. However, the yield was very low and not improved by modification of reaction conditions. Then we have adopted the intramolecular Friedel-Crafts type reaction for construction of the 7-membered ring. We have synthesized acepleiadiene (5, R=H) and acepleiadylene (6, R=H) by the latter method and found 5(R=H) showed a comparable 1^ oxidation peak as that of TTF by CV measurement. Efforts to obtain 1(R=H) via pleiadiene are in progress. Tellurophene-TCNQs (2, n=1, R=H) are only ones left unknown among Hetero-TCNQs, Synthesis of 2 is started from tellurophene. It was converted to 2,5-bis (hydroxymethyl) derivative via 3 reaction steps. Transformation of hydroxymethyl group to dicyanomethylene group to obtain 2 (n=1, R=H) is now actively sudying. Chrysene-TCNQ and -quinone (3) have a unique extended conjugated π-system and are expected to be very stable and have very low coulombic repulsion in their oxidation states. Its synthetic plan through a key intermediate, 2,8- dimethoxychrysene, was progressed. The key compound was obtained in a fairly short steps of reaction and its conversion to 3 is now scrutinized. Phenanthrene-TCNQ and -quinone (4) are unique and assumed to be a strong acceptor, because they have a oquinoid partial structure. Its synthetic plan via 3,6-dibromo- or 3,6-dimethoxy-phenanthrene was executed with success. Both key intermediates were obtained in good yields from the corresponding biphenyls. A green solid compound, which has a very low solubility to common organic solvents, appeared to be 4 (R=C(CN)_2) was obtained by the two successive reactions, substitution of bromine of the former key compound with dicyanomethyl anion and oxidation, We are now actively studying its structure and properties. JA01K
• Development and Synthetic Application of a Novel Type of α-Phosphonocyclobutanones and α-Phosphonoazetidinones

  Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research

  Date (from‐to) : 1998 -1999 

  Author : OKADA Yoshiharu; OGURA Fumio

   

  Recently, the rhodium(II)-catalyzed intramolecular C-H insertion of α-diazo carbonyl compounds has been widely studied and found to be great of value. Reported herein is the synthesis of α-phosphonocyclobutanones bearing 9,10-dihydro-9,10-ethanoanthracene moiety via rhodium(II)-catalyzed intramolecular insertion reaction. 11-Methyl- (3b), 11-ethyl- (3c), and 11-propyl-11-(dimethylphosphono)-acetyl-9,10-dihydro-9,10-ethanoanthracene (3d) were prepared from the Diels-Alder adducts of anthracene and methyl acrylate derivatives, and dimethyl lithiomethylphosphonate in good yields. Α-Diazo β-keto phosphonates 4b-d were readily prepared from 3b-d according to the conventional diazo transfer method by the use of p-toluenesulfonyl azide. Catalytic decomposition of f4b-d was carried out in ClCHィイD22ィエD2CHィイD22ィエD2Cl containing RhィイD22ィエD2(Oac)ィイD24ィエD2 at 80℃ to afford the mixture of cyclobutanones 5b-d and cyclopentanones 6c,d. The stereochemical assignment of 7,8 : 9,10-dibenzo-2-ethyl-4-(dimethylphosphono)tricyclo[4.2.2.0ィイD22,5ィエD2]deca-7,9-dien-3-one (5c) was made on the basis of their ィイD11ィエD1H NMR and IR spectral data. That is, the IR spectrum of 5c shows a peak for carbonyl absorption at 1774.7 cmィイD1-1ィエD1. The ィイD11ィエD1H NMR spectrum of 5c shows a signal for methyl (t, J=4.9 HィイD2ZィエD2, 3H) at δ1.09 and a signal for methine (d, J=3.9 HィイD2ZィエD2, 1H) of 6-position at δ4.51. Accordingly, cyclobutanones were exclusively produced via insertion into the ethane bridge methylene C-H bonds. A similar decomposition of 4b-d with chiral Rh(II) catalysts, such as RhィイD22ィエD2[N-Phtn-(L)-Phe]ィイD24ィエD2 and RhィイD22ィエD2[N-Phth-(L)-Ala]ィイD24ィエD2, afforded the desired optically active 5b-d up to 43%ee. In this reaction, the use of RhィイD22ィエD2[N-Phth-(L)-Phe]ィイD24ィエD2 gave the optically active 5b-d in higher optical yield than that of RhィイD22ィエD2[N-Phth-(L)-Ala]ィイD24ィエD2 irrespective of the kind of alkyl substituents at 11-position of diazo compounds 4b-d.
• SYNTHESES OF NEW ORGANIC ELECTRON DONORS,ACCEPTORS,AND THEIR CHARGE-TRANSFER COMPLEXES,AND STUDIES ON THEIR PROPERTIES

  Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research

  Date (from‐to) : 1997 -1998 

  Author : OGURA Fumio; OKADA Yoshiharu

   

  The target molecules of this research projects are novel organic electron donors (1) and acceptors (2, 3, 4), which are expected to act as effective components to form charge-transfer complexes exhibiting high electric conductivities. The molecule, 1, carries two 7pi electron rings fused to a naplithalenene at its two peri-positions and is expected to behave as a good electron donor in the two stage redox processes. Synthesis of 1 is started from acenaphthene and are first dichiorinated its peri-positins then transformed its 5-membered ring to a cyclic anhydride via bromination with NBS and the following oxidation. The diol obtained by LAH reduction of the anhydride was transformed to 1, 8-Bis(dibromomethyl)4, 5-dichioronaphthalene. The dibromide was reacted with cis-4, 5-bis(boryl)octene, prepared from bis[pinacolato]diboron and 4-octyne, to yield a pleiadene. Efforts to obtain 1 (R=n-Pr) in progress. Tellurophene-TCNQs (2) are only ones left unknown amoung Hetero-TCNQs. Synthesis of 2 is started from tellurophene, which is prepared by 1,4-bis(TMS)-1, 3-butadiyne and Na_2Te and then converted to 2, 5-dicarboxylic acid via 6 steps. Transformation of carboxyl group to dicyanomethylene group to obtain 2 (xl, R=H) is now actively sudying. Crysene-TCNQ (3) has a unique extended conjugated pi-system and expected to be very stable and have very low coulombic repulsion in their oxidation states. Their synthesis are planned to couple a 2-bromo-6-methoxynaphthalene and 2-bromo-5-methoxybenzaldehyde by Suzuki-Miyaura method to yield a key intermediate to lead 2, 8-dimethoxyclirysene. The coupling reaction is now scrutinized. Phenanthrene-TCNQ (4) is unique and assumed to be a strong acceptor, because it has a oquinoid partial structure. Its synthesis is planned to execute via a biphenyl derivative, which is obtained from 2-bromo-5-methoxytoluene and N,N-diethy1-4-methoxybenzamide by a combination of Suzuki-Miyaura and Snieckus coupling methods. The biphenyl derivative is subjected to metalatation, intramnoleculari condensation followed dehydroxylic elimination to afford a key phenanthrene derivative, 3, 6-dimethoxyphenanthrene. Now we are actively investigating coupling reaction conditions and procedures to obtain the biphenyl derivatives. Although we do not yet have the target molecules in our hands, we are closely approaching our targets and very sure to be able to get them in near future.
• 酸性修飾基含有光学活性ホスフィンの開発と触媒的不斉炭素-炭素結合生成反応への利用

  日本学術振興会：科学研究費助成事業

  Date (from‐to) : 1995 -1995 

  Author : 岡田 芳治

   

  本研究では、酸性修飾基としてカルボキシル基を有する新規鎖状光学活性モノホスフィン配位子の開発とそれらのパラジウム錯体触媒を用いた不斉アリリックアルキル化反応への利用について行なった。鎖状光学活性モノホスフィンカルボン酸配位子の合成は次のように行なった。クロトン酸tert-ブチル、4-メチル-2-ペンテン酸tert-ブチル等のα,β-不飽和カルボン酸エステルにTHF溶媒中、n-ブチルリチウム及びHMPA存在下、ジフェニルホスフィンを1,4-付加させ、対応する3-(ジフェニルホスフィノ)ブタン酸tert-ブチル、3-(ジフェニルホスフィノ)-4-メチルペンタン酸tert-ブチルをそれぞれ93%、69%の収率で得た。続いてエステルの酸分解を行ないラセミ体として3-(ジフェニルホスフィノ)ブタン酸(DPBA)、3-(ジフェニルホスフィノ)-4-メチルペンタン酸をそれぞれ71%、42%の収率で得た。得られたラセミ体は光学活性なフェニルエチルアミンを用いた優先晶出法により容易に光学分割できた。この光学活性モノホスフィンカルボン酸配位子と酢酸パラジウムより系中でパラジウム錯体を調製し、酢酸シクロペンテニル、酢酸シクロヘキセニル、酢酸シクロヘプテニル、酢酸シクロオクテニル等の環状酢酸アリルとジエチルホスホノ酢酸エチルとの不斉アルキル化反応を行なった。その結果、従来の配位子と比較して非常に高い不斉収率でアルキル化反応が進行することを見い出した。さらに、環状アリル化合物の環サイズが増大するに従い、不斉収率も向上することが判明した。基質として酢酸シクロオクテニル、配位子にDPBAを用いた時に99%ee以上という最高の不斉収率を得た。
• α-メタロ(シリル,スタニル)ビニルリン化合物の創製と利用

  日本学術振興会：科学研究費助成事業

  Date (from‐to) : 1994 -1994 

  Author : 南 享; 岡田 芳治

   

  α位の典型金属のケイ素、ゲルマニウム、スズ等の官能基を導入したビニルホスホナ-トはビニルシラン、ビニルゲルマン及びビニルスタナンとしての特性とビニルホスホナ-トとしての特性の両反応性を兼ね備えているところから、極めて有用な試薬として期待されるにもかかわらず、未開拓の分野として残されていた。本研究では、 (1)β位にアルキルチオ基(1a,b)、アルコキシ基(1c)、アリール基(1d)等の官能基を有するビニルホスホナ-トを合成した。 (2)合成したビニルホスホナ-トと有機リチウム化合物から、α-リチオビニルホスホナ-トを調製した。続いてアルデヒドとのWittig-Horner反応より、β位にエタンジチオ基及びプロパンジチオ基を有するアレン中間体が生成し、さらにラジカル的な[2+2]シクロ付加反応によりシクロブタン化合物が立体特異的に得られた。 (3)α-リチオビニルホスホナ-トとトリオルガノメタルハライドとの反応により、α-(トリオルガノメタロ)ビニルホスホナ-トを高収率で合成することに成功した。 (4)ビニルシラン、ビニルゲルマンはアシルカチオンと反応して、α-アシルビニルホスホナ-トを高収率で与えた。 (5)α-シリル-β-エトキシビニルホスホナ-トは種々の求核試薬のマイケル付加反応を受け、その後EtO基の脱離を伴い、立体特異的にβ-置換α-(シリン)ビニルホスホナ-トを与えた。 (6)1aよりα-ヨードビニルホスホナ-トの合成に成功した。α-ヨードビニルホスホナ-トはPd触媒存在下、末端アセチレン類と温和な条件で容易に高収率でクロスカップリング生成物を与えた。 以上のごとく、本実験は初期の目的を果たすことに成功したと言える。
• リン官能基の特性を利用する有機合成
• 光学活性・遷移金属錯体を用いる触媒的不斉合成に関する研究
• 不斉ホスフィン配位子の開発
• Study on Catalytic Asymmetric Synthesis Using Optically Active Transition Metal Complexes
• Development of Chiral Phosphine Ligands

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