1989 Fiscal Year Annual Research Report

複合系の反応試剤の開発

Research Project

Project/Area Number	01649008
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, 工学部, 教授 (40001185) 柴崎正勝北海道大学, 薬学部, 教授 (30112767)
Keywords	不斉反応 / 複合系金属試薬 / 選択的反応 / 不斉触媒 / 炭素骨格形成法 / 不斉配位子 / クラスター / 複合系反応試剤
Research Abstract	本研究では、各種金属化合物複合系を基盤とし、新しい反応試剤の開発を目的に研究を進めている。本年度は、以下に述べる新しい金属系反応試剤の創製とその基本的な応用について検討した。 1 スズ、チタン、パラジウム化合物と不斉配位子(キラルなジアミン、ジオール、ホスフィンなど)との複合系キラル錯体の調整と応用について検討し、各種不斉炭素骨格形成法を開発することができた。不斉アルドール、付加環化反応などが極めて高い不斉収率で進行し、生成物がほぼ光学的に純粋に得られる。またHeck反応においても、効果的な不斉誘起が見られることがわかった。さらに、不斉ヒドロホウ素化反応などの不斉官能基化法を見出した。こられの反応は、いずれも触媒量のキラルな複合系反応剤を用いるだけで反応を行うことができ、合成手法としても優れた特徴を持つ。(向山、奈良坂、柴崎、鈴木) 2 炭素骨格形成法についても、複合系金属試剤を活用することによって、特徴ある反応を見出すことができた。ホウ素化合物と遷移金属複合系による立体選択的アリルアルコール合成法、クロム錯体による立体選択的シリルエノールエーテル合成法、マンガン錯体と基質相互作用を利用するラジカル種の分子間付加反応など、選択性の高い炭素骨格形成法を開発した。(鈴木、柴崎、奈良坂) 3 複合系反応剤として新規PtならびにMo,Ruクラスターの合成に成功し、さらに白金錯体がオレフィンのエホキシ化に利用できることが示された。その他、分子識別能を持つ反応剤の開発について、基本的な知見を得ることもできた。(松本、奈良坂)

Research Products

(16 results)

All Other

All Publications (16 results)

[Publications] S.Kobayashi: "Asymmetric Aldol Reaction of Silyl Enol Ethers sith Aldehydes Promoted by the Combined Use of Chiral Diamine Coordinated Tin(II)Triflate and Tributyltin Fluoride." Chem.Lett.297-300 (1989)
[Publications] 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 Ethers with Aidehydes." Chem.Lett.1001-1004 (1989)
[Publications] T.Mukaiyama: "Asyymmetric 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] M.Shibasaki: "Synthesis of cisーBicyclo[4.3.0]Nonー2ーEne Derivatives.The Potent Homoisocarbacyclin Analogs." Chem.Pharm.Bull.37. 1647-1649 (1989)
[Publications] Y.Sato: "Catalytic asymmetric CーC Bond Formation:Asymmetric Synthesis of cisーDecalin Derivatives by PalladiumーCatalyzed Cyclization of Prochiral Alkenyl Idides." J.Org.Chem.54. 4738-4739 (1989)
[Publications] N.Miyaura: "PalladiumーCatalyzed Interーand Intramolecular CrossーCoupling Reactionss of BーAlkylー9ーborabicyclo[3.3.1]nonane Derivatives with lーHaloーlーalkenes or Haloーarenes.Synthesis of Functionalized Alkenes,Arenes,and Cycloalkenes via Hydrobonation Coupling Sequence." J.Am.Chem.Soc.111. 314-321 (1989)
[Publications] A.Suzuki: "New Convenient Approach to the Preparation of(Z)ーAllylic Boronates Via Cyclic 1,4ーHydroboration of 1,3ーDienes with Catecholborane." Tetrahedron Lett.30. 3789-3792 (1989)
[Publications] A.Suzuki: "CrossーCoupling Reaction of Alkylーor Arylboronic Acid Esters with Organic Halides Induced by Thallium(I)Salts and Palladium Catalyst." Chem.Lett.1405-1408 (1989)
[Publications] K.Narasaka: "Asymmetric[2+2]Cycloaddition Reaction Catalyzed by a Chiral Titanium Reagent." Chem.Lett.793-796 (1989)
[Publications] K.Narasaka: "Asymmetric DielsーAlder Reaction Catalyzed by a Chiral Titanium Reagent." J.Am.Chem.Soc.111. 5340-5345 (1989)
[Publications] K.Narasaka: "Asymmetric Intramolecular DielsーAlder Reaction Catalyzed by the Chiral Titanium Reagent." Chem.Lett.1947-1950 (1989)
[Publications] K.Narasaka: "The Addition Reaction ofーKeto Carboxylic Acids to Olefinic Compounds by the Use Mn(III)Tris(2ーpyridinecarboxylate)as an Oxidant." Chem.Lett.2169-2172 (1989)
[Publications] K.Matsumoto: "MixedーValent Octanuclear Platinum Accetamide Complex,[Pt_8(NH_3)_<16>(C_2H_4NO)_8]1o+" J.Am.Chem.Soc.111. 3074-3075 (1989)
[Publications] K.Matsumoto: "Crystal Structure and ^<13>C and ^<195>Pt NMR Spectra of anαーPyrrolidonateーBinuclear Platinum(II)Complex,[Pt_2(NH_3)_4(C_4H_6NO)_2]_2(PF_6)_3(NO_3).H_2O" Inorg.Chem.28. 2959-2964 (1989)
[Publications] K.Matsumoto: "Synthesis,Chemical Properties and Antitumor Complexes." Inorg.Biochem. 36. (1989)
[Publications] K.Matsumoto: "Crystal Structure and ^<13>C NMR of αーPhrrolidonatoーbridged [Pt(III)_2(NH_3)_4(C_4H_6NO)_2(NO_2)(NO_3)](NO_3)_2.H_2O and Conversion of the Binuclear into Tetranuclear Complexe on Electrochemical Redox Reaction." Chem.Lett.1857-1860 (1989)

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

[Publications] 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 Ethers with Aidehydes." Chem.Lett.1001-1004 (1989)

[Publications] T.Mukaiyama: "Asyymmetric 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] M.Shibasaki: "Synthesis of cisーBicyclo[4.3.0]Nonー2ーEne Derivatives.The Potent Homoisocarbacyclin Analogs." Chem.Pharm.Bull.37. 1647-1649 (1989)

[Publications] Y.Sato: "Catalytic asymmetric CーC Bond Formation:Asymmetric Synthesis of cisーDecalin Derivatives by PalladiumーCatalyzed Cyclization of Prochiral Alkenyl Idides." J.Org.Chem.54. 4738-4739 (1989)

[Publications] A.Suzuki: "New Convenient Approach to the Preparation of(Z)ーAllylic Boronates Via Cyclic 1,4ーHydroboration of 1,3ーDienes with Catecholborane." Tetrahedron Lett.30. 3789-3792 (1989)

[Publications] A.Suzuki: "CrossーCoupling Reaction of Alkylーor Arylboronic Acid Esters with Organic Halides Induced by Thallium(I)Salts and Palladium Catalyst." Chem.Lett.1405-1408 (1989)

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

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

[Publications] K.Narasaka: "Asymmetric Intramolecular DielsーAlder Reaction Catalyzed by the Chiral Titanium Reagent." Chem.Lett.1947-1950 (1989)

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

[Publications] K.Matsumoto: "MixedーValent Octanuclear Platinum Accetamide Complex,[Pt_8(NH_3)_<16>(C_2H_4NO)_8]1o+" J.Am.Chem.Soc.111. 3074-3075 (1989)

[Publications] K.Matsumoto: "Crystal Structure and ^<13>C and ^<195>Pt NMR Spectra of anαーPyrrolidonateーBinuclear Platinum(II)Complex,[Pt_2(NH_3)_4(C_4H_6NO)_2]_2(PF_6)_3(NO_3).H_2O" Inorg.Chem.28. 2959-2964 (1989)

[Publications] K.Matsumoto: "Synthesis,Chemical Properties and Antitumor Complexes." Inorg.Biochem. 36. (1989)

[Publications] K.Matsumoto: "Crystal Structure and ^<13>C NMR of αーPhrrolidonatoーbridged [Pt(III)_2(NH_3)_4(C_4H_6NO)_2(NO_2)(NO_3)](NO_3)_2.H_2O and Conversion of the Binuclear into Tetranuclear Complexe on Electrochemical Redox Reaction." Chem.Lett.1857-1860 (1989)

向山光昭東京理科大学, 理学部, 教授 (60016003)