1991 Fiscal Year Annual Research Report

複合系の反応試剤の開発

Research Project

Project/Area Number	03215107
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)	松本和子早稲田大学, 理工学部, 教授 (60111457) 奈良坂紘一東京大学, 理学部, 教授 (50016151) 鈴木章北海道大学, 薬学部, 教授 (40001185) 柴崎正勝東京大学, 薬学部, 教授 (30112767)
Keywords	不斉触媒反応 / 不斉アルド-ル反応 / 不斉ヘック反応 / 不斉付加環化反応 / 有機ホウ素化合物 / 金属酸化剤 / 一電子酸化
Research Abstract	各種金属化合物を中心とする複合系の形成を基盤とし,優れた特徴を持つ反応試剤の開発とその一般化を行うとともに有用な化合物合成への応用についても検討を行った。 1.不斉触媒反応の開発光学活性ジアミン配位子を持つスズ(II)トリフラ-トを触媒とする,不斉アルド-ル反応の一般化をはかり、様々な光学活性アルド-ルを高い光学純度で得ることができた。又、希士類アルコキシドが塩基触媒として、アルド-ル,マイケル,シアノシリル化反応等に有効であることを見い出し,特にニトロアルド-ル反応において,触媒量の光学活性ランタンアルコキシドを用いるだけで,良好な光学収率でアルド-ル体を得ることができた。又,前年度開発した不斉Heak反応を利用し,カプネレン類の合成中間体の不斉合成を行った。さらにキラルな1,4ージオ-ルで修飾したチタン化合物を用いる不斉〔2+2〕付加環化反応の一般化をはかり,巾広い適用性を持つことを明らかにした。 2.高選択的な反応試剤の開発パラジウム触媒を用いる有機ホウ素化合物とビニルあるいはアリ-ルハライドとのカップリング反応を利用し、ヘテロ芳香族化合物,α,βー不飽和ケトン,シクロアルケン類の一般的合成法を確立した。一方,有機化合物の一電子酸化による活性化を基盤とし,シクロプロパノ-ル,エナミン,2ースタンニルー1,3ージチアンなどと,オレフィンとの分子間クロスカップリング反応を見い出した。さらに白金あるいはルテニウム多核錯体の合成を行い,オレフィンの酸素酸化が高い選択性で進行することも明らかになった。

Research Products

(27 results)

All Other

All Publications (27 results)

[Publications] T.Mukaiyama,T.Takashima,M.Katsurada,and H.Aizawa: "A Highly Stereoselective Synthesis of αーGlucosides from 1ー0ーAcetyl Glucose by Use of Tin(IV)ChlorideーSilver Perchlorate Catalyst System" Chem.Lett.1991. 533-536 (1991)
[Publications] S.Kobayashi,Y.Tsuchiya,and T.Mukaiyama: "Enantioselective Addition Reaction of Trimethylsilyl Cyanide with Aldehydes Using a Chiral Tin(II)Lewis Acid" Chem.Lett.1991. 541-544 (1991)
[Publications] S.Kobayashi,T.Uchiro,Y.Fujishita,I.Shiina,and T.Mukaiyama: "Asymmetric Aldol Reaction between Achiral Silyl Enol Ethers and Achotal Aldehydes by Use of a Chiral Promoter System" J.Am.Chem.Soc.113. 4247-4252 (1991)
[Publications] T.Mukaiyama,M.Katsurada,and T.Takashima: "The Evaluation of Catalysts Generated from Lewis Acids and Silver Perchlorate in a Highly Stereoselective Glycosylation of 1ー0ーAcetylーDーGlulcose" Chem.Lett.1991. 985-988 (1991)
[Publications] T.Mukaiyama,T.Ohno,T.Nishimura,S.Suda,and S.Kobayashi: "The Catalytic FriedelーCrafts Acylation Reaction Using a Catalyst Generated from GaCl_3 and a Silver Salt" Chem.Lett.1991. 1059-1062 (1991)
[Publications] S.Kobayashi,M.Furuya,A.Ohtsubo,and T.Mukaiyama: "Catalytic Asymmetric aldol Reaction of the Silyl enol Ether of Acetic Acid Thioester with Aldehydes Using Chiral Tin(II) Lewis Acid" Tetrahedron:Asymmetry. 2. 635-638 (1991)
[Publications] S.Satoh,M.Sodeoka,H.Sasai,and M.Shibasaki: "Control of RingーJunction Stereochemistry via Radical Cyclization.A New Construction of transーHydrindans" J.Org.Chem.56. 2278-2280 (1991)
[Publications] K.Kagechika,M.Shibasaki: "Asymmetric Heck Reaction:A Catalytic Synthesis of the Key Intermediate for △^<9(12)>ーCapnelleneー3β,8β,10αーtriol and △^<9(12)>ーCapnelleneー3β,8β,10α,14ーtetrol" J.Org.Chem.56. 4093-4094 (1991)
[Publications] H.Yamada,M.Sodeoka,and M.Shibasaki: "A New Method for the Stereocontrolled Synthesis of Dienamine Derivatives Using (Naphthalene)chromium Tricarbonyl Catalyzed Isomerezation" J.Org.Chem.56. 4569-4574 (1991)
[Publications] N.Miyachi,H.Satoh,and M.Shibasaki: "The Binary Reagent PhSeSePhーCuOTf:a Useful Phenylselenylating Agent" J.Chem.Soc.,Perkin Trans.1. 2049-2050 (1991)
[Publications] T.Suzuki,y.Uozumi,and M.Shibasaki: "A Catalytic Asymmetric Synthesis of αーMethylene Lactones by the Palladiumーcatalysed Carbonylation of Prochiral Alkenyl Halides" J.Chem.Soc.,Chem.Commun.1991. 1593-1595 (1991)
[Publications] A.Suzuki: "Synthetic Studies via the CrossーCoupling Reaction of Organoboron Derivatives with Organic Halides" Pure&Appl.Chem.63. 419-422 (1991)
[Publications] T.Ishiyama,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzed Carbonylative Crossーcoupling Reaction of 1ーHaloー1ーalkenes with 9ーAlky1ー9ーBBN Derivatives.A Direct Synthesis of α,βーUnsaturated Ketones" Bull.Chem.Soc.Jpn.64. 1999-2001 (1991)
[Publications] S.Hara and A.Suzuki: "The Organic Synthesis Using Haloboration Reaction 20.A simple Synthesis of(2ーBromoally)diphenoxyborane by the Bromoboration of Allene and its Reaction with Carbonyl Compounds" Tetrahedron Lett.32. 6749-6752 (1991)
[Publications] T.Ishiyama,N.Miyaura,and A.suzuki: "Synthesis of Functionalized Organotin Compounds via PalladiumーCatalyzed CrossーCoupling Reaction of Aryl or 1ーalkenyl Halides with 9ー〔R_3Sn(CH_3)_n〕ー9ーBBN(n=2,3,and4)Derivatives" Synlett.687-688 (1991)
[Publications] T.Ishiyama,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzed Carbonylative CrossーCoupling Reaction of Iodoalkanes with 9ーAlkylー9ーBBN Derivatives" Tetrahedron Lett.32. 6923-6926 (1991)
[Publications] K.Narasaka,K.Iwakura,and T.Okauchi: "Addition Reaction of Cation Radicals of Nitroalkanes to Olefinic Compounds by the Use of Manganese(III)2ーPyridinecarboxylate." Chem.Lett.1991. 423-426 (1991)
[Publications] K.Narasaka and T.Okauchi: "Generation of Cation Radicals from Allylic Sulfide and Their Reactions with Silyl Enol Ethers by the Use of Cerium(IV)Ammonium Nitrate." Chem.Lett.1991. 515-518 (1991)
[Publications] K.Narasaka,H.Kusama,and Y.Hayashi: "Enantioーand Diastereoーselective Synthesis of(+)ーGrandisol" Bull.Chem.Soc.Jpn.64. 1471-1478 (1991)
[Publications] N.Iwasawa,S.Hayakawa,K.Isobe,and K.Narasaka: "Generation of βーKeto Radicals from Cyclopropanol Derivatives by the Use of Manganese(III)2ーPyridinecarboxylate as an Oxidant and Their Reactions with Olefins" Chem.Lett.1991. 1193-1196 (1991)
[Publications] Y.Hayashi,K.Otaka,N.Saito,and K.Narasaka: "Asymmetric Reactions of Enamines with Methyl(E)ー4ー0xoー4ー(2ーoxoー1,3ーoxazolidinー3ーy1)ー2ーbutenoate by the Use of a Chiral Titanium Reagent" Bull.Chem.Soc.Jpn.64. 2122-2127 (1991)
[Publications] k.Narasaka,M.Saito,and N.Iwasawa: "Asymmetric Synthesis of the Hydronaphthalene Moieties of Mevinic Acids" Tetrahedron:Asymmetry. 2. 1305-1318 (1991)
[Publications] M.Kato,M.Kawano,H.Taniguchi,M.Funaki,H.Moriyama,T.Sato,and K.Matsumoto: "Syntheses,Structures,and Reactivities of the SulfurーBridged Trinuclear Complexes〔(L)Ru(CO)(PPh_3)〕_2(μーMS_4)(L=PhNCHS,CH_2CH_2ー(C_2H_4N),CH_2CH_2C(0)OMe;M=Mo).Photochemical and Chemical Reactions and Isolation of a Trinuclear Complex Having a Coordinatively Unーsaturated Ruthenium Atom" Inorg.Chem.31. 26-35 (1992)
[Publications] K.Sakai and K.Matsumoto: "Oxidation of Benzene to Phenol with Hydrogen Peroxide Catalyzed by αーPyrrolidonateーBridged MixedーValent Tetranuclear Platinum Complexes" J.Mol.CATal.67. 7-18 (1991)
[Publications] K.sakai,K.Matsumoto,and K.Nishio: "Crystal Structure of 2ーFluoroacetamidatoーBridged MixedーValent Octanuclear Platinum Blue with Average Platinum Oxidation State of 2.08,〔Pt_8(NH_3)_<16>(CH_2FCONH)_8〕(NO_3)_<8。66°>4H_2O" Chem.Lett.1991. 1081-1084 (1991)
[Publications] K.Matsumoto and K.Haraトhima: "A.Tetranuclear Tervalent Platinum Complex with αーPyrrolidonate and Deprotonated Ammine Bridging Ligands,〔(NO_3)(NH_3)_2Pt(C_4H_6NO)_2ー Pt(NH_3)(μーNH_2)〕_2(NO_3)_4" Inorg.Chem.30. 3032-3234 (1991)
[Publications] H.Urata,H.Moriyama,and K.Matsumoto: "Synthesis,Crystal Structure,and Solvolysis Reaction of HーT 3,3ーDimethylglutarimidateーBinuclear Platinum(II)Complex,〔Pt_2(NH_3)_4(C_7H_<10>NO_2)_2〕(NO_3)_2・H_2O" Inorg.Chem.30. 3914-3919 (1991)

1991 Fiscal Year Annual Research Report

複合系の反応試剤の開発

Principal Investigator

向山 光昭 東京理科大学, 理学部, 教授 (60016003)

Research Products

[Publications] T.Mukaiyama,T.Takashima,M.Katsurada,and H.Aizawa: "A Highly Stereoselective Synthesis of αーGlucosides from 1ー0ーAcetyl Glucose by Use of Tin(IV)ChlorideーSilver Perchlorate Catalyst System" Chem.Lett.1991. 533-536 (1991)

[Publications] S.Kobayashi,Y.Tsuchiya,and T.Mukaiyama: "Enantioselective Addition Reaction of Trimethylsilyl Cyanide with Aldehydes Using a Chiral Tin(II)Lewis Acid" Chem.Lett.1991. 541-544 (1991)

[Publications] S.Kobayashi,T.Uchiro,Y.Fujishita,I.Shiina,and T.Mukaiyama: "Asymmetric Aldol Reaction between Achiral Silyl Enol Ethers and Achotal Aldehydes by Use of a Chiral Promoter System" J.Am.Chem.Soc.113. 4247-4252 (1991)

[Publications] T.Mukaiyama,M.Katsurada,and T.Takashima: "The Evaluation of Catalysts Generated from Lewis Acids and Silver Perchlorate in a Highly Stereoselective Glycosylation of 1ー0ーAcetylーDーGlulcose" Chem.Lett.1991. 985-988 (1991)

[Publications] T.Mukaiyama,T.Ohno,T.Nishimura,S.Suda,and S.Kobayashi: "The Catalytic FriedelーCrafts Acylation Reaction Using a Catalyst Generated from GaCl_3 and a Silver Salt" Chem.Lett.1991. 1059-1062 (1991)

[Publications] S.Kobayashi,M.Furuya,A.Ohtsubo,and T.Mukaiyama: "Catalytic Asymmetric aldol Reaction of the Silyl enol Ether of Acetic Acid Thioester with Aldehydes Using Chiral Tin(II) Lewis Acid" Tetrahedron:Asymmetry. 2. 635-638 (1991)

[Publications] S.Satoh,M.Sodeoka,H.Sasai,and M.Shibasaki: "Control of RingーJunction Stereochemistry via Radical Cyclization.A New Construction of transーHydrindans" J.Org.Chem.56. 2278-2280 (1991)

[Publications] K.Kagechika,M.Shibasaki: "Asymmetric Heck Reaction:A Catalytic Synthesis of the Key Intermediate for △^<9(12)>ーCapnelleneー3β,8β,10αーtriol and △^<9(12)>ーCapnelleneー3β,8β,10α,14ーtetrol" J.Org.Chem.56. 4093-4094 (1991)

[Publications] H.Yamada,M.Sodeoka,and M.Shibasaki: "A New Method for the Stereocontrolled Synthesis of Dienamine Derivatives Using (Naphthalene)chromium Tricarbonyl Catalyzed Isomerezation" J.Org.Chem.56. 4569-4574 (1991)

[Publications] N.Miyachi,H.Satoh,and M.Shibasaki: "The Binary Reagent PhSeSePhーCuOTf:a Useful Phenylselenylating Agent" J.Chem.Soc.,Perkin Trans.1. 2049-2050 (1991)

[Publications] T.Suzuki,y.Uozumi,and M.Shibasaki: "A Catalytic Asymmetric Synthesis of αーMethylene Lactones by the Palladiumーcatalysed Carbonylation of Prochiral Alkenyl Halides" J.Chem.Soc.,Chem.Commun.1991. 1593-1595 (1991)

[Publications] A.Suzuki: "Synthetic Studies via the CrossーCoupling Reaction of Organoboron Derivatives with Organic Halides" Pure&Appl.Chem.63. 419-422 (1991)

[Publications] T.Ishiyama,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzed Carbonylative Crossーcoupling Reaction of 1ーHaloー1ーalkenes with 9ーAlky1ー9ーBBN Derivatives.A Direct Synthesis of α,βーUnsaturated Ketones" Bull.Chem.Soc.Jpn.64. 1999-2001 (1991)

[Publications] S.Hara and A.Suzuki: "The Organic Synthesis Using Haloboration Reaction 20.A simple Synthesis of(2ーBromoally)diphenoxyborane by the Bromoboration of Allene and its Reaction with Carbonyl Compounds" Tetrahedron Lett.32. 6749-6752 (1991)

[Publications] T.Ishiyama,N.Miyaura,and A.suzuki: "Synthesis of Functionalized Organotin Compounds via PalladiumーCatalyzed CrossーCoupling Reaction of Aryl or 1ーalkenyl Halides with 9ー〔R_3Sn(CH_3)_n〕ー9ーBBN(n=2,3,and4)Derivatives" Synlett.687-688 (1991)

[Publications] T.Ishiyama,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzed Carbonylative CrossーCoupling Reaction of Iodoalkanes with 9ーAlkylー9ーBBN Derivatives" Tetrahedron Lett.32. 6923-6926 (1991)

[Publications] K.Narasaka,K.Iwakura,and T.Okauchi: "Addition Reaction of Cation Radicals of Nitroalkanes to Olefinic Compounds by the Use of Manganese(III)2ーPyridinecarboxylate." Chem.Lett.1991. 423-426 (1991)

[Publications] K.Narasaka and T.Okauchi: "Generation of Cation Radicals from Allylic Sulfide and Their Reactions with Silyl Enol Ethers by the Use of Cerium(IV)Ammonium Nitrate." Chem.Lett.1991. 515-518 (1991)

[Publications] K.Narasaka,H.Kusama,and Y.Hayashi: "Enantioーand Diastereoーselective Synthesis of(+)ーGrandisol" Bull.Chem.Soc.Jpn.64. 1471-1478 (1991)

[Publications] N.Iwasawa,S.Hayakawa,K.Isobe,and K.Narasaka: "Generation of βーKeto Radicals from Cyclopropanol Derivatives by the Use of Manganese(III)2ーPyridinecarboxylate as an Oxidant and Their Reactions with Olefins" Chem.Lett.1991. 1193-1196 (1991)

[Publications] Y.Hayashi,K.Otaka,N.Saito,and K.Narasaka: "Asymmetric Reactions of Enamines with Methyl(E)ー4ー0xoー4ー(2ーoxoー1,3ーoxazolidinー3ーy1)ー2ーbutenoate by the Use of a Chiral Titanium Reagent" Bull.Chem.Soc.Jpn.64. 2122-2127 (1991)

[Publications] k.Narasaka,M.Saito,and N.Iwasawa: "Asymmetric Synthesis of the Hydronaphthalene Moieties of Mevinic Acids" Tetrahedron:Asymmetry. 2. 1305-1318 (1991)

[Publications] K.Sakai and K.Matsumoto: "Oxidation of Benzene to Phenol with Hydrogen Peroxide Catalyzed by αーPyrrolidonateーBridged MixedーValent Tetranuclear Platinum Complexes" J.Mol.CATal.67. 7-18 (1991)

[Publications] K.sakai,K.Matsumoto,and K.Nishio: "Crystal Structure of 2ーFluoroacetamidatoーBridged MixedーValent Octanuclear Platinum Blue with Average Platinum Oxidation State of 2.08,〔Pt_8(NH_3)_<16>(CH_2FCONH)_8〕(NO_3)_<8。66°>4H_2O" Chem.Lett.1991. 1081-1084 (1991)

[Publications] K.Matsumoto and K.Haraトhima: "A.Tetranuclear Tervalent Platinum Complex with αーPyrrolidonate and Deprotonated Ammine Bridging Ligands,〔(NO_3)(NH_3)_2Pt(C_4H_6NO)_2ー Pt(NH_3)(μーNH_2)〕_2(NO_3)_4" Inorg.Chem.30. 3032-3234 (1991)

[Publications] H.Urata,H.Moriyama,and K.Matsumoto: "Synthesis,Crystal Structure,and Solvolysis Reaction of HーT 3,3ーDimethylglutarimidateーBinuclear Platinum(II)Complex,〔Pt_2(NH_3)_4(C_7H_<10>NO_2)_2〕(NO_3)_2・H_2O" Inorg.Chem.30. 3914-3919 (1991)

向山光昭東京理科大学, 理学部, 教授 (60016003)