1989 Fiscal Year Annual Research Report

有機化学における複合系の高次制御

Research Project

Project/Area Number	01649007
Research Institution	Tokyo University of Science
Principal Investigator	向山光昭東京理科大学, 理学部, 教授 (60016003)
Co-Investigator(Kenkyū-buntansha)	伊藤嘉彦京都大学, 工学部, 教授 (40026018) 桑嶋功東京工業大学, 理学部, 教授 (50016086) 奈良坂紘一東京大学, 理学部, 教授 (50016151) 大野雅二東京大学, 薬学部, 教授 (00111550) 桜井英樹東北大学, 理学部, 教授 (70025873)
Keywords	複合系高次制御 / 複合系の構造化学的アプローチ / 複合系の反応論的アプローチ / 複合系の分子機能 / 複合系の反応試剤 / 複合系の反応設計 / 複合系の反応制御 / 有機合成化学
Research Abstract	有機化合物における特異な物性、反応性あるいは反応の選択性を、単分子的にあるいは直接反応に関与する分子間相互作用のレベルで理解するこれまでの捉え方に加えて、分子とそれを取り巻く環境を複合的に把握し、有機分子が示す種々の物理的および化学的現象を、有機、無機、生物など関連諸分野の研究者の参加のもとに、総合的な観点から解明することを目的として研究を行った。総括班は、各班における、1)複合系の構造化学的アプローチ、2)複合系の反応論的アプローチ、3)複合系の分子機能、4)複合系の反応試剤、5)複合系の反応設計、6)複合系の反応制御、などの研究を、総括班会議、班長会議を通じて、総合的に取りまとめ、推進した。平成元年11月20、21の2日間、大阪において第1回の公開シンポジウムを開催し、全班員に加えて各大学、企業から73名の参加を得て盛大に行われた。本シンポジウムでは、各研究班の班長が、班会議での活発な討議をもとに、それぞれの班の研究計画について総合的な説明を行い、引き続き各班の計画班員および公募班員から、加納航治、村上幸人、細見彰、山本明夫、鳥居滋、奈良坂紘一、竜田邦明、山本嘉則、金岡祐一、光延旺洋、板井昭子、斉藤烈、大野雅二の各氏が、各自の研究計画および成果について報告し、熱心な討議が行われた。また、全班員の研究成果について取りまとめた研究成果報告書を刊行し、関係各位に配布した。次年度のシンポジウムとして、第2回を6月に東京で、第3回を12月に仙台で開催することに決定し、準備を開始した。

Research Products
(47 results)

All Other

All Publications (47 results)

[Publications] S.Kobayashi: "Asymmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes Promoted by the Combined Use of Chiral Diamine Coordinated Tin(II)Triflate and Tributyltin Fluoride," Chem.Lett.297-300 (1989)
[Publications] K.Homma: "Convenient Synthesis of Disubstituted Cyclic Ethers. Synthesis of(-)-cis-Rose Oxide and(cis-6-Methyltetrahydropyran-2-y1)acetic Acid" Chem.Lett.893-896 (1989)
[Publications] T.Mukaiyama: "Effective Activation of Carbonyl and Related Compounds with Phosphonium Salts.The Aldol and Michael Reactions of Carbonyl Compounds with Silyl Nucleophiles and Alkyl Enol Ethers" Chem.Lett.993-996 (1989)
[Publications] T.Mukaiyama: "Efficient Activation of Acetals toward Nucleophiles by the Use of Transition Metal Salts.New Method for Cyanation of Acetals and Orthoester Derived from Aromatic and α,βーUnsaturated Carbonyl Comppounds with Trimethylsilyl Cyanide under Neutral Condition" Chem.Lett.997-1000 (1989)
[Publications] T.Mukaiyama: "Perfect Stereochemical Control in the Synthesis of synーαーMethylーβーhydroxy Thioesters by Asmmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes" Chem.Lett.1001-1004 (1989)
[Publications] T.Mukaiyama: "[1,2ーBenzenediolato(2ー)ーO,O]oxotitanium.A Mild and Efficitent Catalyst for the Michael Reaction of Ketene Silyl Acetals with α,βーUnsaturated Ketones" Chem.Lett.1171-1174 (1989)
[Publications] T.Mukaiyama: "Efficient Activation of Acetals toward Nucleophiles with[Rh(COD)Cl]_2Catalyst.New Method for the Preparation of Aldols from Acetals and Silyl Enol Ethers by the Combined Use of Catalytic Amounts of[Rh(COD)Cl]_2 and Trimethysilyl Cyanide" Chem.Lett.1273-1276 (1989)
[Publications] T.Mukaiyama: "The Addition Reaction of Acetals(Aldehydes)to Simple Olefins by the Use of a New Catalyst System" Chem.Lett.1277-1280 (1989)
[Publications] S.Kobayashi: "Asymmetric Aldolーtype Reaction between Both Achiral Ketene Silyl Acetals and Aldehydes by the Use of a Chiral Promoter" Chem.Lett.1319-1322 (1989)
[Publications] T.Mukaiyama: "A Convenient Synthesis of βーAminoesters.The Reaction of Imines with Ketene Silyl Acetals Catalyzed by Phosphonium Salts" Chem.Lett.1397-1400 (1989)
[Publications] T.Mukaiyama: "Reductive Cross Cupling Reaction of a Glyoxylate with Carbonyl Compounds.A Facile Synthesis of α,βーDihydroxycarboxylate Based on a Low Valent Titanium Compound" Chem.Lett.1401-1404 (1989)
[Publications] R.Hara: "[1,2ーBenzenediolato(2ー)ーO,O]oxotitanium.A Chemoselective and Efficient Catalyst for,Aldolーtype Reaction of Ketene Silyl Acetals with Aldehydes" Chem.Lett.1909-1912 (1989)
[Publications] S.Kobayashi: "A Highly Enantioselective Synthesis of 2ーSubstituted Malates by Asymmetric Aldol Reaction" Chem.Lett.2069-2072 (1989)
[Publications] T.Mukaiyama: "Catalytic Aymmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes by the Use of Chiral Diamine Coordinated Tin(II)triflate" Chem.Lett.129-132 (1990)
[Publications] K.Honma: "Stereoselective Addition of tーButyldimethylsiloxyー1ーethoxyethene to 2ーTrichloromethylー1,3ーdioxaneー4ーones" Chem.Lett.161-164 (1990)
[Publications] M.Kira: "Preparation of Xーray Crystal Structure of the First Pentacoordinate Silysilicates" J.Am.Chem.Soc.111. 3747 (1989)
[Publications] A.Sekiguchi: "Isolation and characterization of 1,2ーdilithio〔tetrakisー(trimethysilyl)〕ethane" J.Am.Chem.Soc.111. 3748 (1989)
[Publications] K.Sakamoto: "Novel Anionic Polymerization of Masked Disilenes to Polysilane High Polymers and Block Copolymers" J.Am.Chem.Soc.111. 7641 (1989)
[Publications] K.Sato,: "Allylation of αーHydroxy Ketones with Allyltrimethylsilanes and Allyltrialkoxysilanes in the Presence of Triethylamire.Stereochemical Regulation Involving Chelated Bicyclic Transition States" J.Am.Chem.Soc.111. 6429 (1989)
[Publications] M.Kira: "ESR Study of 2ーSubstituted 2ーAdamantyl Radicals.Configuration and Longーrange Hyperfine Interaction" J.Am.Chem.Soc.111. 8256 (1989)
[Publications] H.Sakurai: "Metamorphosis of Synthetic Strategies with Allylic Sidlanes: Tetracoordinated Allylic Silanes into Pentacoordinated Allylic Silicates" Synlett.1. 1 (1989)
[Publications] M.Kira: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media. Discrimination between Linear and alphaーbranched Alkanols" J.Am.Chem.Soc.112. 257 (1990)
[Publications] M.Otsuka: "Manーdesigned Bleomycin with Altered Sequence Specificity in DNA Cleavage" J.Am.Chem.Soc.112. 838-845 (1990)
[Publications] A.Suga: "TransitionーMetal Binding Site of Bleomycin.A Synthetic AnalogueSuperior to Bleomycin Dioxygen Activating Capability" Synlett.1. 70-71 (1989)
[Publications] Y.Kaku: "Chiral Environment around the Metal Center Obderved by the Epoxidation with the Iron Complex of Bleomycin and the Synthetic Analogue" Chem.Lett.611-614 (1989)
[Publications] Y.Ichikawa: "Selective βーCーand βーSーGlycosylation of 2ーDeoxyribofuranose Derivatives Controlled by the 3ーHydroxy Protecting Group" Bull.Chem.Soc.Jpn.62. 845-852 (1989)
[Publications] Y.Hayashi: "Asymmetric[2+2]Cycloaddition Reaction Catalyzed by a Chiral Titanium Reagent" Chem.Lett.793-796 (1989)
[Publications] T.Okauchi: "Stereoselective Synthesis of βー2ーDeoxyribonucleosides from 1ー0ーAcetylー3ー0ー[2ー(methylsulfinyl)ethyl]ー2ーdexyribose" Chem.Lett.801-804 (1989)
[Publications] K.Narasaka: "Kinetic Resolution of αーArylcarboxylic Acid Derivatives by a Catalytic Use of a Chiral Titanium Alkoxide" Chem.Lett.1187-1190 (1989)
[Publications] K.Narasaka: "Asymmetric DielsーAlder Reaction Catalyzed by a Chiral Titanium Regent" J.Am.Chem.Soc.111. 5340-5345 (1989)
[Publications] N.Iwasawa: "Characterization of the Chiral Titanium Reagent Prepared from Tartrateーderived Chiral Diol and Titanium Dichloride Diisopropoxide" Chem.Lett.1581-1584 (1989)
[Publications] N.Iwasawa: "Asymmetric Intramolecular DielsーAlder Reaction Catalyzed bythe Chiral Titanium Reagent" Chem.Lett.1974-1950 (1989)
[Publications] K.Narasaka: "The Addition Reaction of βーKeto Carboxylic Acids to Olefinic Compounds by the Use of Mn(III)Tris(2ーpyridinecarboxylate)as an Oxidant" Chem.Lett.2169-2172 (1989)
[Publications] Y.Ichikawa: "Enatioー and Diastereoselective Synthesis of Carbocyclic Oxetanocin Analogs" J.Chem.Soc.,Chem.Commun.(1990)
[Publications] S.Matsuzawa: "ChlorosilaneーAccerelated Conjugate Addition of Catalytic and Stoichiometric Organocopper Reagents" Tetrahedron. 45. 349 (1989)
[Publications] S.Matsuzawa: "Me_3SiClーAssisted 1,2ーAddition of Organocuprates to Carbonyl Compounds" Tetrahedron Lett.30. 1975 (1989)
[Publications] Y.Horiguchi: "Double Hydroxylation of Enol Sily Ethers.A SingleーStep Synthesis of αーα',ーDihydroxy Ketones" Tetrahedron Lett.30. 3324 (1989)
[Publications] Y.Horiguchi: "Regioselective Synthesis of Two Types of Cyclic 3ー(Trimethylsilylmethyl)ーenones" Tetrahedron Lett.30. 3327 (1989)
[Publications] Y.Horiguchi: "Total Synthesis of(+)ーCortisone.Double Hydroxylation Reaction for Corticoid Synthesis" J.Am.Chem.Soc.111. 6257 (1989)
[Publications] T.Matsuda: "A Selective OneーCarbon Ring Expansion Reaction of 1ーSilーoxycycloalkanecarbaldehydes Catalyzed by a Lewis Acid" Tetrahedron Lett.30. 4267 (1989)
[Publications] Y.Horiguchi: "A Highly Efficient EightーMembered Ring Cyclization for Construction of Taxane Carbon Framework" J.Am.Chem.Soc.111. 8277 (1989)
[Publications] S.Aoki: "Palladiumーand PlatinumーCatalyzed Reaction of Siloxycyclopropanes with Acid Chlorides.A Homoenolate Route to 1,4ーDicarbonyl Compounds" Tetrahedron Lett.30. 6541 (1989)
[Publications] K.Tanino: "SiliconーBased Nucleophiles Mediated OneーCarbon Ring Enlargement Reactions of 1ー(Trimethylsilymethyl)ーcycloalkanecarboaldehydes" Tetrahedron Lett.30. 6551 (1989)
[Publications] T.Hayashi: "Asymmetric Synthesis Catalyzed by Chiral FerrocenylrhosphineーTransitionーMetal complexes.8.Palladium Catalyzed Asymmetric Allylic Amination" J.Am.Chem.Soc.111. 6301-6311 (1989)
[Publications] K.Tamao: "Nickel(O)ーCatalyzed Cyclization of 1,7ーDiynes via Hydrosilation:Oneーstep Synthesis of 1,2ーDialkylidenecyclohexanes with a (Z)ーVinylsilane Moiety" J.Am.Chem.Soc.111. 6478-6480 (1989)
[Publications] Y.Ito: "Synthesis of Asymmetric Dialkynyl Imines.Stepwise Coupling of NーPhenyl(phenylthio)imidoyl Chloride with Alkyltin Compounds" Chem.Lett.1261-1264 (1989)
[Publications] T.Mukaiyama: "Challenges in Synthetic Organic Chemistry(International Series of Monographs on Chemistry No.20)" Oxford University Press, 240 (1990)

1989 Fiscal Year Annual Research Report

有機化学における複合系の高次制御

Principal Investigator

向山 光昭 東京理科大学, 理学部, 教授 (60016003)

Research Products

[Publications] S.Kobayashi: "Asymmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes Promoted by the Combined Use of Chiral Diamine Coordinated Tin(II)Triflate and Tributyltin Fluoride," Chem.Lett.297-300 (1989)

[Publications] K.Homma: "Convenient Synthesis of Disubstituted Cyclic Ethers. Synthesis of(-)-cis-Rose Oxide and(cis-6-Methyltetrahydropyran-2-y1)acetic Acid" Chem.Lett.893-896 (1989)

[Publications] T.Mukaiyama: "Effective Activation of Carbonyl and Related Compounds with Phosphonium Salts.The Aldol and Michael Reactions of Carbonyl Compounds with Silyl Nucleophiles and Alkyl Enol Ethers" Chem.Lett.993-996 (1989)

[Publications] T.Mukaiyama: "Perfect Stereochemical Control in the Synthesis of synーαーMethylーβーhydroxy Thioesters by Asmmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes" Chem.Lett.1001-1004 (1989)

[Publications] T.Mukaiyama: "[1,2ーBenzenediolato(2ー)ーO,O]oxotitanium.A Mild and Efficitent Catalyst for the Michael Reaction of Ketene Silyl Acetals with α,βーUnsaturated Ketones" Chem.Lett.1171-1174 (1989)

[Publications] T.Mukaiyama: "Efficient Activation of Acetals toward Nucleophiles with[Rh(COD)Cl]_2Catalyst.New Method for the Preparation of Aldols from Acetals and Silyl Enol Ethers by the Combined Use of Catalytic Amounts of[Rh(COD)Cl]_2 and Trimethysilyl Cyanide" Chem.Lett.1273-1276 (1989)

[Publications] T.Mukaiyama: "The Addition Reaction of Acetals(Aldehydes)to Simple Olefins by the Use of a New Catalyst System" Chem.Lett.1277-1280 (1989)

[Publications] S.Kobayashi: "Asymmetric Aldolーtype Reaction between Both Achiral Ketene Silyl Acetals and Aldehydes by the Use of a Chiral Promoter" Chem.Lett.1319-1322 (1989)

[Publications] T.Mukaiyama: "A Convenient Synthesis of βーAminoesters.The Reaction of Imines with Ketene Silyl Acetals Catalyzed by Phosphonium Salts" Chem.Lett.1397-1400 (1989)

[Publications] T.Mukaiyama: "Reductive Cross Cupling Reaction of a Glyoxylate with Carbonyl Compounds.A Facile Synthesis of α,βーDihydroxycarboxylate Based on a Low Valent Titanium Compound" Chem.Lett.1401-1404 (1989)

[Publications] R.Hara: "[1,2ーBenzenediolato(2ー)ーO,O]oxotitanium.A Chemoselective and Efficient Catalyst for,Aldolーtype Reaction of Ketene Silyl Acetals with Aldehydes" Chem.Lett.1909-1912 (1989)

[Publications] S.Kobayashi: "A Highly Enantioselective Synthesis of 2ーSubstituted Malates by Asymmetric Aldol Reaction" Chem.Lett.2069-2072 (1989)

[Publications] T.Mukaiyama: "Catalytic Aymmetric Aldol Reaction of Silyl Enol Ethers with Aldehydes by the Use of Chiral Diamine Coordinated Tin(II)triflate" Chem.Lett.129-132 (1990)

[Publications] K.Honma: "Stereoselective Addition of tーButyldimethylsiloxyー1ーethoxyethene to 2ーTrichloromethylー1,3ーdioxaneー4ーones" Chem.Lett.161-164 (1990)

[Publications] M.Kira: "Preparation of Xーray Crystal Structure of the First Pentacoordinate Silysilicates" J.Am.Chem.Soc.111. 3747 (1989)

[Publications] A.Sekiguchi: "Isolation and characterization of 1,2ーdilithio〔tetrakisー(trimethysilyl)〕ethane" J.Am.Chem.Soc.111. 3748 (1989)

[Publications] K.Sakamoto: "Novel Anionic Polymerization of Masked Disilenes to Polysilane High Polymers and Block Copolymers" J.Am.Chem.Soc.111. 7641 (1989)

[Publications] K.Sato,: "Allylation of αーHydroxy Ketones with Allyltrimethylsilanes and Allyltrialkoxysilanes in the Presence of Triethylamire.Stereochemical Regulation Involving Chelated Bicyclic Transition States" J.Am.Chem.Soc.111. 6429 (1989)

[Publications] M.Kira: "ESR Study of 2ーSubstituted 2ーAdamantyl Radicals.Configuration and Longーrange Hyperfine Interaction" J.Am.Chem.Soc.111. 8256 (1989)

[Publications] H.Sakurai: "Metamorphosis of Synthetic Strategies with Allylic Sidlanes: Tetracoordinated Allylic Silanes into Pentacoordinated Allylic Silicates" Synlett.1. 1 (1989)

[Publications] M.Kira: "Highly Stereoselective Allylation of Aldehydes with Pentacoordinate Allylsilicates in Hydroxylic Media. Discrimination between Linear and alphaーbranched Alkanols" J.Am.Chem.Soc.112. 257 (1990)

[Publications] M.Otsuka: "Manーdesigned Bleomycin with Altered Sequence Specificity in DNA Cleavage" J.Am.Chem.Soc.112. 838-845 (1990)

[Publications] A.Suga: "TransitionーMetal Binding Site of Bleomycin.A Synthetic AnalogueSuperior to Bleomycin Dioxygen Activating Capability" Synlett.1. 70-71 (1989)

[Publications] Y.Kaku: "Chiral Environment around the Metal Center Obderved by the Epoxidation with the Iron Complex of Bleomycin and the Synthetic Analogue" Chem.Lett.611-614 (1989)

[Publications] Y.Ichikawa: "Selective βーCーand βーSーGlycosylation of 2ーDeoxyribofuranose Derivatives Controlled by the 3ーHydroxy Protecting Group" Bull.Chem.Soc.Jpn.62. 845-852 (1989)

[Publications] Y.Hayashi: "Asymmetric[2+2]Cycloaddition Reaction Catalyzed by a Chiral Titanium Reagent" Chem.Lett.793-796 (1989)

[Publications] T.Okauchi: "Stereoselective Synthesis of βー2ーDeoxyribonucleosides from 1ー0ーAcetylー3ー0ー[2ー(methylsulfinyl)ethyl]ー2ーdexyribose" Chem.Lett.801-804 (1989)

[Publications] K.Narasaka: "Kinetic Resolution of αーArylcarboxylic Acid Derivatives by a Catalytic Use of a Chiral Titanium Alkoxide" Chem.Lett.1187-1190 (1989)

[Publications] K.Narasaka: "Asymmetric DielsーAlder Reaction Catalyzed by a Chiral Titanium Regent" J.Am.Chem.Soc.111. 5340-5345 (1989)

[Publications] N.Iwasawa: "Characterization of the Chiral Titanium Reagent Prepared from Tartrateーderived Chiral Diol and Titanium Dichloride Diisopropoxide" Chem.Lett.1581-1584 (1989)

[Publications] N.Iwasawa: "Asymmetric Intramolecular DielsーAlder Reaction Catalyzed bythe Chiral Titanium Reagent" Chem.Lett.1974-1950 (1989)

[Publications] K.Narasaka: "The Addition Reaction of βーKeto Carboxylic Acids to Olefinic Compounds by the Use of Mn(III)Tris(2ーpyridinecarboxylate)as an Oxidant" Chem.Lett.2169-2172 (1989)

[Publications] Y.Ichikawa: "Enatioー and Diastereoselective Synthesis of Carbocyclic Oxetanocin Analogs" J.Chem.Soc.,Chem.Commun.(1990)

[Publications] S.Matsuzawa: "ChlorosilaneーAccerelated Conjugate Addition of Catalytic and Stoichiometric Organocopper Reagents" Tetrahedron. 45. 349 (1989)

[Publications] S.Matsuzawa: "Me_3SiClーAssisted 1,2ーAddition of Organocuprates to Carbonyl Compounds" Tetrahedron Lett.30. 1975 (1989)

[Publications] Y.Horiguchi: "Double Hydroxylation of Enol Sily Ethers.A SingleーStep Synthesis of αーα',ーDihydroxy Ketones" Tetrahedron Lett.30. 3324 (1989)

[Publications] Y.Horiguchi: "Regioselective Synthesis of Two Types of Cyclic 3ー(Trimethylsilylmethyl)ーenones" Tetrahedron Lett.30. 3327 (1989)

[Publications] Y.Horiguchi: "Total Synthesis of(+)ーCortisone.Double Hydroxylation Reaction for Corticoid Synthesis" J.Am.Chem.Soc.111. 6257 (1989)

[Publications] T.Matsuda: "A Selective OneーCarbon Ring Expansion Reaction of 1ーSilーoxycycloalkanecarbaldehydes Catalyzed by a Lewis Acid" Tetrahedron Lett.30. 4267 (1989)

[Publications] Y.Horiguchi: "A Highly Efficient EightーMembered Ring Cyclization for Construction of Taxane Carbon Framework" J.Am.Chem.Soc.111. 8277 (1989)

[Publications] S.Aoki: "Palladiumーand PlatinumーCatalyzed Reaction of Siloxycyclopropanes with Acid Chlorides.A Homoenolate Route to 1,4ーDicarbonyl Compounds" Tetrahedron Lett.30. 6541 (1989)

[Publications] K.Tanino: "SiliconーBased Nucleophiles Mediated OneーCarbon Ring Enlargement Reactions of 1ー(Trimethylsilymethyl)ーcycloalkanecarboaldehydes" Tetrahedron Lett.30. 6551 (1989)

[Publications] T.Hayashi: "Asymmetric Synthesis Catalyzed by Chiral FerrocenylrhosphineーTransitionーMetal complexes.8.Palladium Catalyzed Asymmetric Allylic Amination" J.Am.Chem.Soc.111. 6301-6311 (1989)

[Publications] K.Tamao: "Nickel(O)ーCatalyzed Cyclization of 1,7ーDiynes via Hydrosilation:Oneーstep Synthesis of 1,2ーDialkylidenecyclohexanes with a (Z)ーVinylsilane Moiety" J.Am.Chem.Soc.111. 6478-6480 (1989)

[Publications] Y.Ito: "Synthesis of Asymmetric Dialkynyl Imines.Stepwise Coupling of NーPhenyl(phenylthio)imidoyl Chloride with Alkyltin Compounds" Chem.Lett.1261-1264 (1989)

[Publications] T.Mukaiyama: "Challenges in Synthetic Organic Chemistry(International Series of Monographs on Chemistry No.20)" Oxford University Press, 240 (1990)

向山光昭東京理科大学, 理学部, 教授 (60016003)