1990 年度実績報告書

複合系の反応試剤の開発

研究課題

研究課題/領域番号	02231107
研究機関	東京理科大学
研究代表者	向山光昭東京理科大学, 理学部, 教授 (60016003)
研究分担者	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) 柴崎正勝北海道大学, 薬学部, 教授 (30112767)
キーワード	反応試剤 / 反応制御 / 不斉触媒反応 / クロスカップリング反応 / 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
研究概要	各種金属化合物と有機化合物との複合系の形成を基盤とした、優れた特徴をもつ反応試剤の開発について検討した。以下にその成果をまとめる。 1、不斉触媒の開発(向山、柴崎、奈良坂) 光学活性ジアミン配位子をもつスズ(II)トリフラ-トを触媒とする不斉アルド-ル反応が、プロピオニトリル中で効率良く進行し、高い不斉収率で対応する付加体を与えることが明らかになった。各種Synーαー置換ーβーヒどロキシエステル,Synーα,βージヒドロキシエステルが、極めて高い光学純度で合成できる。さらに、パラジウムのキラルなジホスフィス錯体が、分子内ヘック反応、πーアリルパラジウムのアルキル化反応の不斉触媒となり、種々の2環性化合物を良好な不斉収率で合成することに成功した。一方、キラルなルイス酸触媒の開発についても検討され、キラルな1,4ジオ-ルで修飾したチタン化合物が、[4+2],[2+2]付加環化反応の優れた不斉触媒となることを明らかにした。 2、高選択的な反応試剤の開発(鈴木、奈良橋、松本) 有機ホウ素化合物と芳香族あるいはビニルトリフラ-トとのクロスカップリング反応がリン酸カリウムの存在下パラジウム触媒を用いると、すみやかに進行し、オレフィン、ジエン、ビアリ-ル類が立体選択的に、合成できる。一方、有機化合物の一電子酸化による活性化を基盤とし、ニトロ化合物、βーケト酸、アリルスルフィドなどと、オレフィンとの分子間クロスカップリング反応を見出すことができた。さらに、混合原子価白金錯体を用いることによって、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ている。

研究成果
(22件)

すべてその他

すべて文献書誌 (22件)

[文献書誌] T.Mukaiyama: "Effective Activation of Carbonyl and Related Compounds with Phosphonium Salts.The Aldol and Michael Reactions of Carbonyl compounds with silyl Nucelophiles and Alkyl Enol Ethers." Chem.Lett。. 1989. 993-996 (1989)
[文献書誌] T.Mukaiyama: "Perfect Stereochemical Control in the Synthesis of synーαーMethylーβーhydroxy Thioesters by Asymmetric Aldol Reaction of Silyl Enol Esters with Aldehydes." Chem.Lett.1989. 1001-1004 (1989)
[文献書誌] T.Mukaiyama: "An Efficient Chiral Promoter in the Aldolーtype Reaction.Chiral Diamine Cooridinated Tin(II) TriflateーDibutyltindiacetate Complex." Chem.Lett.1989. 1757-1760 (1989)
[文献書誌] T.Mukaiyama: "Catalytic Asymmetric Aldol Reaction of Silyl Enol Esthers with Aldehydes by the Use of Chiral Diamine Coordinated Tin(II) Triflate." Chem.Lett.1990. 129-132 (1990)
[文献書誌] T.Mukaiyama: "[1,1'ーBiー2ーnaphtahlenediolate(2ー)ーO,O']oxotitanium.An Efficient Chiral Catalyst for the Asymmetric Aldol Reaction of Silyl Enol Esthers with Aldehydes." Chem.Lett.1990. 1015-1018 (1990)
[文献書誌] T.Mukaiyama: "A New Efficient Chiral Catalyst System.Combined Use of Tin(II) Oxide,Trimethylsilyl Triflate and Chiral Diamine in Asymmetric Aldol Reaction." Chem.Lett.1991. 1147-1150 (1990)
[文献書誌] M.Sodeoka,H.Yamada and M.Shibasaki: "A New Method for the Stereocontrolled Synthesis of Silyl Dienol Ethers Using(Naphthalene)chromium Tricarbonyl Catalyzed Isomerization." J.Am.Chem.Soc.112. 4906-4911 (1990)
[文献書誌] Y.Sato,M.Sodeoka,and M.Shibasaki: "On the Role of Silver Salts in Asymmetric Heckーtype Reaction.A Greatly Improved Catalytic Asymmetric Synthesis of cisーDecalin Derivatives." Chem。Lett.1990. 1953-1954 (1990)
[文献書誌] H.Sasai,Y.Kirio,M.Shibasaki: "Zr(OーtーBu)_4,an Efficient and Convenient Basic Reagent in Organic Synthesis.Utilization in Cross and Intramolecular Aldol Reaction." J.Org.Chem.55. 5306-5308 (1990)
[文献書誌] M.Mori,N.Uesaka,and M.Shibasaki: "Ring Constuction by Zirconiumーpromoted Reductive Coupling of Nitriles with Alkenes." J.Chem.Soc.,Chem.Commun.1990. 1222-1224 (1990)
[文献書誌] N.Yamashina,S.Hyuga S.Hara,and A.Suzuki: "Organic Synthesis Using Haloboration Reaction 18.A Stereoselective Synthesis of βーMonoーand β,βーDisubstituted α,βーUnsaturated Esters." Tetrahedron Lett. 30. 6555-6558 (1989)
[文献書誌] S.Sato,N.Miyaura,and A.Suzuki: "Rhodium(I)ーCatalyzed Asymmetric Hydroboration of Alkenes with 1,2,3ーBenzodioxaborole." Tetrahedron Lett.31. 231-234 (1990)
[文献書誌] T.Ohーe,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzad CrossーCoupling Reactions of Aryl or Vinylic Triflates with Organoboron Compounds." Synlett. 1990. 221-223 (1990)
[文献書誌] A.Suzuki: "Synthetic Studies on the CrossーCoupling Reaction of Organoboron Derivatives with Organic Halides." Pure & Appl.Chem.63. 419-425 (1991)
[文献書誌] T.Ishiyama,N.Miyaura,and A.Suzuki: "Palladium(O)ーCatalyzed Reaction of 9ーAlkylー9ーborabicyclo[3.3.1]nonane with 1ーBromoー1ーPhenylthioethene;4ー(3ーChclohexenyl)ー2ーPhenylthioー1ーbutene." Organic Syntheses.
[文献書誌] K.Narasaka,H.Sakurai T.Kato,and N.Iwasawa: "Synthesis of Bidentate Lewis Acids and Their Properties as Host Molecules." Chem.Lett.1990. 1271-1274 (1990)
[文献書誌] Y.Hayashi and K.Narasaka: "Asymmetric[2+2] Cycloaddition Reaction Between α,βーUnsaturated Acid Derisatives and Alkynyl or Alkenyl Sulfides Catalyzed by a Chiral Titanium Reagent." Chem.Lett.1990. 1295-1298 (1990)
[文献書誌] K.Narasaka,Y.Tanaka and F.Kanai: "Asymmetric DielsーAlder Reaction of an Acrylic Acid Derivative Using a Chiral Titanium Catalyst." Bull.Chem.Soc.Jpn.
[文献書誌] K.Narasaka,K.Iwakuma 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. 423-446 (1991)
[文献書誌] 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)
[文献書誌] K.Matsumoto,H.Moriyama and K.Suzuki: "Crystal Structure of HeadーtoーHead Bis(μーαーpyridonatoーN,O)bis[(ethylenediamine)ーpalladium] Nitrate,[Pd_2(en)_2(C_5H_4ーNO)_2](NO_3)_2,and ^<13>C and ^1Hー ^<13>C COSY NMR Study of HeadーtoーHead to HeadーtoーTail Isomerization in Solution." Inorg.Chem.29. 2096-2100 (1990)
[文献書誌] K.Sakai and K.Matsumoto: "Homogeneous Catalysis of Platinum Blue Related Complexes in Photoreduction of Water into Hydrogen." J.Mol.Catal.62. 1-14 (1990)

1990 年度 実績報告書

複合系の反応試剤の開発

研究代表者

向山 光昭 東京理科大学, 理学部, 教授 (60016003)

研究成果

[文献書誌] T.Mukaiyama: "Effective Activation of Carbonyl and Related Compounds with Phosphonium Salts.The Aldol and Michael Reactions of Carbonyl compounds with silyl Nucelophiles and Alkyl Enol Ethers." Chem.Lett。. 1989. 993-996 (1989)

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

[文献書誌] T.Mukaiyama: "An Efficient Chiral Promoter in the Aldolーtype Reaction.Chiral Diamine Cooridinated Tin(II) TriflateーDibutyltindiacetate Complex." Chem.Lett.1989. 1757-1760 (1989)

[文献書誌] T.Mukaiyama: "Catalytic Asymmetric Aldol Reaction of Silyl Enol Esthers with Aldehydes by the Use of Chiral Diamine Coordinated Tin(II) Triflate." Chem.Lett.1990. 129-132 (1990)

[文献書誌] T.Mukaiyama: "[1,1'ーBiー2ーnaphtahlenediolate(2ー)ーO,O']oxotitanium.An Efficient Chiral Catalyst for the Asymmetric Aldol Reaction of Silyl Enol Esthers with Aldehydes." Chem.Lett.1990. 1015-1018 (1990)

[文献書誌] T.Mukaiyama: "A New Efficient Chiral Catalyst System.Combined Use of Tin(II) Oxide,Trimethylsilyl Triflate and Chiral Diamine in Asymmetric Aldol Reaction." Chem.Lett.1991. 1147-1150 (1990)

[文献書誌] M.Sodeoka,H.Yamada and M.Shibasaki: "A New Method for the Stereocontrolled Synthesis of Silyl Dienol Ethers Using(Naphthalene)chromium Tricarbonyl Catalyzed Isomerization." J.Am.Chem.Soc.112. 4906-4911 (1990)

[文献書誌] Y.Sato,M.Sodeoka,and M.Shibasaki: "On the Role of Silver Salts in Asymmetric Heckーtype Reaction.A Greatly Improved Catalytic Asymmetric Synthesis of cisーDecalin Derivatives." Chem。Lett.1990. 1953-1954 (1990)

[文献書誌] H.Sasai,Y.Kirio,M.Shibasaki: "Zr(OーtーBu)_4,an Efficient and Convenient Basic Reagent in Organic Synthesis.Utilization in Cross and Intramolecular Aldol Reaction." J.Org.Chem.55. 5306-5308 (1990)

[文献書誌] M.Mori,N.Uesaka,and M.Shibasaki: "Ring Constuction by Zirconiumーpromoted Reductive Coupling of Nitriles with Alkenes." J.Chem.Soc.,Chem.Commun.1990. 1222-1224 (1990)

[文献書誌] N.Yamashina,S.Hyuga S.Hara,and A.Suzuki: "Organic Synthesis Using Haloboration Reaction 18.A Stereoselective Synthesis of βーMonoーand β,βーDisubstituted α,βーUnsaturated Esters." Tetrahedron Lett. 30. 6555-6558 (1989)

[文献書誌] S.Sato,N.Miyaura,and A.Suzuki: "Rhodium(I)ーCatalyzed Asymmetric Hydroboration of Alkenes with 1,2,3ーBenzodioxaborole." Tetrahedron Lett.31. 231-234 (1990)

[文献書誌] T.Ohーe,N.Miyaura,and A.Suzuki: "PalladiumーCatalyzad CrossーCoupling Reactions of Aryl or Vinylic Triflates with Organoboron Compounds." Synlett. 1990. 221-223 (1990)

[文献書誌] A.Suzuki: "Synthetic Studies on the CrossーCoupling Reaction of Organoboron Derivatives with Organic Halides." Pure & Appl.Chem.63. 419-425 (1991)

[文献書誌] T.Ishiyama,N.Miyaura,and A.Suzuki: "Palladium(O)ーCatalyzed Reaction of 9ーAlkylー9ーborabicyclo[3.3.1]nonane with 1ーBromoー1ーPhenylthioethene;4ー(3ーChclohexenyl)ー2ーPhenylthioー1ーbutene." Organic Syntheses.

[文献書誌] K.Narasaka,H.Sakurai T.Kato,and N.Iwasawa: "Synthesis of Bidentate Lewis Acids and Their Properties as Host Molecules." Chem.Lett.1990. 1271-1274 (1990)

[文献書誌] Y.Hayashi and K.Narasaka: "Asymmetric[2+2] Cycloaddition Reaction Between α,βーUnsaturated Acid Derisatives and Alkynyl or Alkenyl Sulfides Catalyzed by a Chiral Titanium Reagent." Chem.Lett.1990. 1295-1298 (1990)

[文献書誌] K.Narasaka,Y.Tanaka and F.Kanai: "Asymmetric DielsーAlder Reaction of an Acrylic Acid Derivative Using a Chiral Titanium Catalyst." Bull.Chem.Soc.Jpn.

[文献書誌] K.Narasaka,K.Iwakuma 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. 423-446 (1991)

[文献書誌] 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)

[文献書誌] K.Sakai and K.Matsumoto: "Homogeneous Catalysis of Platinum Blue Related Complexes in Photoreduction of Water into Hydrogen." J.Mol.Catal.62. 1-14 (1990)

1990 年度実績報告書

向山光昭東京理科大学, 理学部, 教授 (60016003)