1994 Fiscal Year Annual Research Report

多段階反応における立体制御の機構

Research Project

Project/Area Number	04403006
Research Institution	KYOTO UNIVERSITY
Principal Investigator	大野惇吉京都大学, 化学研究所, 教授 (70027077)
Co-Investigator(Kenkyū-buntansha)	岡村睦雄新潟大学, 理学部・化学科, 助教授 (30215503) 畑安雄京都大学, 化学研究所, 助教授 (10127277) 河合靖京都大学, 化学研究所, 助手 (20240830)
Keywords	立体選択性 / スルフィニル基 / カルボニル基 / 軸不斉 / NAD / 立体化学 / 酸化 / 還元
Research Abstract	カルボニル基やスルフィニル基のように、極性のある置換基を分子内にもち、その極性基の配向によって軸不斉が規定され、キラル面を有する化合物を合成した。その内で、いくつかは室温でラセミ化を起こす不安定な不斉であったが、その知見を元にデザインした化合物2種は安定な不斉を与えることが判明した。ヨード塩を用いたX線結晶構造解析を行なった結果、2,3-dihydro2,2,54-trimethylthieno[3,2-b]pyridinium 1-oxideについては異常分散法を利用して絶対構造を求める事ができた。また、6,7-dihydro-6-methyl-5-oxo-N-methyl-pyridino[3,3-d]-2-benzazepiniumはD-camphorsulfonateとのジアステレオマ-塩として、その絶対構造を求めた。MM3を基礎とした分子軌道法を用いて算出したこれらの化合物の構造は、X線結晶構造解析によって求めた絶対構造を極めて良く再現している。従って、未だに構造が確定していない化合物についても、分子軌道法による計算の結果をかなりの確度で信用することができそうである。この種の化合物にキラル面を有する還元剤を反応させると、中間に生成する電子移動錯体にはジアステレオ異性体が生ずることになる。つまり、組合せによって4種の電子移動錯体が生成する。その生成比を測定することによって、いかなるジアステレオ関係が最もエネルギー的に安定であるかを判断することができる。その結果、極性部位どうしが重なり合う構造が先ず優先的に生成するが、その中では、双極子置換基が存在するエナンチオ面から還元剤の攻撃を受ける構造が優先的に形成されることが明らかになった。極性基によって反応の立体化学が支配される例は、これまで報告されたことはない。

Research Products
(18 results)

All Other

All Publications (18 results)

[Publications] T.Kimura,T.Maruyama,A.Ohno et al.: "Structural Effect on Chilation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type Chelators" Bull.Chem.Soc.Jpn.67. 1615-1621 (1994)
[Publications] K.Nakamura,M.Kinoshita A.Ohno: "Effect of Solvent on Lipase-Catalyged Transesterification in Organic Medeia" Tetrahedron. 50. 4681-4690 (1994)
[Publications] Y.Kawai,S.Kondo,A.Ohno et al.: "Stereochemical Control in Microbial Reduction.23.Thermal Treatment of Bakers′ Yeast for Controlling the....." Bull.Chem.Soc.Jpn.67. 2244-2247 (1994)
[Publications] S.Yasui,N.Fujii,A.Ohno et al.: "Mechanism of Dediazoniation of Arenediazonium Salts with Triphenylphosphine and Trialkyl Phosphites.Generation of......" J.Chem.Soc.,Perkin Trans.2. 177-183 (1994)
[Publications] I.Nakamura,Y.Inoue,A.Ohno: "Enantioselective Microbial Oxidation of 1-Arylethanol in an Organic Solvent" Tetrahedron Lett.35. 4375-4376 (1994)
[Publications] S.Yasui,K.Shioji,A.Ohno: "Reactivity of a Phosphoranyl Radical Generated by Photoreaction of Phenyl Diphenylphosphinite with 10-Methylacridinium....." Heteroatom Chem.5. 85-90 (1994)
[Publications] S.Yasui,K.Shioji,A.Ohno: "Reaction of a Cation Radical Generated from Trivalent Phosphorus Compound through Single-Electron Transfer to Arenediazonium Sdlt" Tetrahedron Lett.35. 2695-2698 (1994)
[Publications] A.Ohno,A.Tsutsumi,Y Kawai et al: "NAD(P)^+-NAD(P)H Models.83.Molecular Asymmetry with a Carbonyl Croup:Electronically Controlled Stereochemistry in the...." J.Am.Chem.Soc.116. 8133-8137 (1994)
[Publications] K.Nakamura,M.Kawasaki,A.Ohno: "Effects of Substrate on Lipase-Catalyzed Transesterification of ω-Substituted 1-Alkanols in Organic Solvents" Bull.Chem.Soc.Jpn.67. 3053-3056 (1994)
[Publications] M.Uemura,H.Nishimura,A.Ohno et al.: "Kinetic Resolution of Hydroxymethyl-Substituted(Arene)Cr(CO)_3 and (Diene)Fe(CO)_3 sy Lipase" Tetrahedron:Asymmetry. 5. 1673-1282 (1994)
[Publications] K.Nakamura,S.Kondo,A.Ohno et al: "Purification and Characterization of α-Keto Ester Reductases from Bakers′ Yeast" Biosci.Biotech.Biochem.58. 2236-2240 (1994)
[Publications] A.Ohno,J.Kunitomo,T.Kawamoto,et al.: "Variation of Reaction Channel in a Flavoenzyme Model with a Modified Pyrimidine Ring" Tetrahedron Lett.35. 9729-9732 (1994)
[Publications] T.Kimura,T.Maruyama,A.Ohno.et al.: "1,2-Bis(o-aminophenoxy)ethane-N,O,N′,N′-tetraacetic Acid Derivatives on Complexation with Lanthanoid Metal Tons....." Heteroatom Chem.6(in press). (1995)
[Publications] A.Ohno,N.Yamazaki,M.Okamura,et al.: "NAD(P)^+-NAD(P)H Models.84.Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Croup" Heteroatom chem.6(in press). (1995)
[Publications] Y.Kawai,K.Takanobe,A.OHno: "Stereothemical Control in Microbial Reduction.25.Additives Controlling Diastereoselectivity in a Microbial Reduction...." Bull.Chem.Soc.Jpn.68. 285-288 (1995)
[Publications] K.Ndkamura,Y.Inoue,A.Ohno: "Improvement of Enantioselectivity of Microbial Reduction by Usiug Organic solvent Redox Coupler System" Tetrahedron Lett.36. 265-266 (1995)
[Publications] Y.Kawai,K.Hida,K.Nakamura,A.Ohno: "Introduction of Plural Asymmetric Centers by a β-Keto Ester Reductase from Bakers′Yeast" Tetrahedron Lett.36. 591-592 (1995)
[Publications] K.Nakamura,S.Kondo,N.Nakajima,A.Ohno: "Mechanistic Study jor Stereochemical Control of Microbial Reduction of d-Keto Esters in an Orgnaic Solvent" Tetrahedron. 51(in press). (1995)

1994 Fiscal Year Annual Research Report

多段階反応における立体制御の機構

Principal Investigator

大野 惇吉 京都大学, 化学研究所, 教授 (70027077)

Research Products

[Publications] T.Kimura,T.Maruyama,A.Ohno et al.: "Structural Effect on Chilation Selectivity of Alkaline Earth Metal Ions with Aminopolycarboxylate-Type Chelators" Bull.Chem.Soc.Jpn.67. 1615-1621 (1994)

[Publications] K.Nakamura,M.Kinoshita A.Ohno: "Effect of Solvent on Lipase-Catalyged Transesterification in Organic Medeia" Tetrahedron. 50. 4681-4690 (1994)

[Publications] Y.Kawai,S.Kondo,A.Ohno et al.: "Stereochemical Control in Microbial Reduction.23.Thermal Treatment of Bakers′ Yeast for Controlling the....." Bull.Chem.Soc.Jpn.67. 2244-2247 (1994)

[Publications] S.Yasui,N.Fujii,A.Ohno et al.: "Mechanism of Dediazoniation of Arenediazonium Salts with Triphenylphosphine and Trialkyl Phosphites.Generation of......" J.Chem.Soc.,Perkin Trans.2. 177-183 (1994)

[Publications] I.Nakamura,Y.Inoue,A.Ohno: "Enantioselective Microbial Oxidation of 1-Arylethanol in an Organic Solvent" Tetrahedron Lett.35. 4375-4376 (1994)

[Publications] S.Yasui,K.Shioji,A.Ohno: "Reactivity of a Phosphoranyl Radical Generated by Photoreaction of Phenyl Diphenylphosphinite with 10-Methylacridinium....." Heteroatom Chem.5. 85-90 (1994)

[Publications] S.Yasui,K.Shioji,A.Ohno: "Reaction of a Cation Radical Generated from Trivalent Phosphorus Compound through Single-Electron Transfer to Arenediazonium Sdlt" Tetrahedron Lett.35. 2695-2698 (1994)

[Publications] A.Ohno,A.Tsutsumi,Y Kawai et al: "NAD(P)^+-NAD(P)H Models.83.Molecular Asymmetry with a Carbonyl Croup:Electronically Controlled Stereochemistry in the...." J.Am.Chem.Soc.116. 8133-8137 (1994)

[Publications] K.Nakamura,M.Kawasaki,A.Ohno: "Effects of Substrate on Lipase-Catalyzed Transesterification of ω-Substituted 1-Alkanols in Organic Solvents" Bull.Chem.Soc.Jpn.67. 3053-3056 (1994)

[Publications] M.Uemura,H.Nishimura,A.Ohno et al.: "Kinetic Resolution of Hydroxymethyl-Substituted(Arene)Cr(CO)_3 and (Diene)Fe(CO)_3 sy Lipase" Tetrahedron:Asymmetry. 5. 1673-1282 (1994)

[Publications] K.Nakamura,S.Kondo,A.Ohno et al: "Purification and Characterization of α-Keto Ester Reductases from Bakers′ Yeast" Biosci.Biotech.Biochem.58. 2236-2240 (1994)

[Publications] A.Ohno,J.Kunitomo,T.Kawamoto,et al.: "Variation of Reaction Channel in a Flavoenzyme Model with a Modified Pyrimidine Ring" Tetrahedron Lett.35. 9729-9732 (1994)

[Publications] T.Kimura,T.Maruyama,A.Ohno.et al.: "1,2-Bis(o-aminophenoxy)ethane-N,O,N′,N′-tetraacetic Acid Derivatives on Complexation with Lanthanoid Metal Tons....." Heteroatom Chem.6(in press). (1995)

[Publications] A.Ohno,N.Yamazaki,M.Okamura,et al.: "NAD(P)^+-NAD(P)H Models.84.Stereochemistry Controlled by the Electronic Effect from a Sulfinyl Croup" Heteroatom chem.6(in press). (1995)

[Publications] Y.Kawai,K.Takanobe,A.OHno: "Stereothemical Control in Microbial Reduction.25.Additives Controlling Diastereoselectivity in a Microbial Reduction...." Bull.Chem.Soc.Jpn.68. 285-288 (1995)

[Publications] K.Ndkamura,Y.Inoue,A.Ohno: "Improvement of Enantioselectivity of Microbial Reduction by Usiug Organic solvent Redox Coupler System" Tetrahedron Lett.36. 265-266 (1995)

[Publications] Y.Kawai,K.Hida,K.Nakamura,A.Ohno: "Introduction of Plural Asymmetric Centers by a β-Keto Ester Reductase from Bakers′Yeast" Tetrahedron Lett.36. 591-592 (1995)

[Publications] K.Nakamura,S.Kondo,N.Nakajima,A.Ohno: "Mechanistic Study jor Stereochemical Control of Microbial Reduction of d-Keto Esters in an Orgnaic Solvent" Tetrahedron. 51(in press). (1995)

大野惇吉京都大学, 化学研究所, 教授 (70027077)