1995 Fiscal Year Annual Research Report

不斉空間の構築

Research Project

Project/Area Number	05234104
Research Institution	The University of Tokyo
Principal Investigator	古賀憲司東京大学, 薬学部, 教授 (10012600)
Co-Investigator(Kenkyū-buntansha)	中村栄一東京大学, 大学院・理学系研究科, 教授 (00134809) 富岡清大阪大学, 産業科学研究所, 教授 (50114575) 向山光昭東京理科大学, 理学部, 教授 (60016003) 富士薫京都大学, 化学研究所, 教授 (20027056)
Keywords	キラルリチウムアミド / 不斉α-アルキル化反応 / グリコシル化反応 / キラルホスフィンアミド / 不斉共役付加反応 / イミン / キレーション制御反応
Research Abstract	1.単配座型キラルリチウムアミドを設計合成し、この結晶構造をX線で、溶液構造を多核NMRで解析し明らかにした。更に、その不斉脱プロトン化反応における高不斉誘起の発現にははリチウムブロミドの存在が不可欠であることが判明し、その会合状態の解析にも成功した. 2.α-アミノ酸のα位不斉炭素のみを不斉源とする不斉α-アルキル化を検討している。既にN-メチルアミノ酸誘導体については〜88%eeでα-アルキル化が進行することを見出しているが、今回除去が容易な窒素置換基(MEM基、ピバロイルオキシメチル基)を持つα-アミノ酸誘導体の不斉α-アルキル化反応(〜75%ee)の開発に成功した. 3.糖質を不斉源として有機合成に利用することを考え、グリコシドを高収率、高立体選択的に得る手法の開発を目的として研究を行い、遊離の糖と遊離のアルコールを用いるα及びβ選択的グリコシル化反応を見出すことができた. 4.キラル不斉補助剤を組み込んだ不飽和カルボニル化合物へのフェニルチオールのジアステレオ面選択的付加反応が、金属塩の有無、また種類によって大きく影響を受け、その事実を基盤としてジアステレオ面の任意選択に成功した.一方、キラルホスフィンアミドを配位子として用いるグリニヤール試薬の不斉共役付加反応が、触媒量の第一銅と触媒量のキラル配位子の存在下円滑に進行し、高い不斉収率と化学反応で共役付加体を与えることを見出した. 5.従来成功例の少ないイミンへのエナンチオ選択的付加反応について検討し、不斉配位子をもつアリル亜鉛化合物のcis-イミンへの付加で高選択性を実現した.またab initio量子力学計算によりキレーション制御反応の制御要因を明らかにした。

Research Products
(15 results)

All Other

All Publications (15 results)

[Publications] Kenji Koga: "Approaches to Catalytic Asymmetic Formation and Reactions of Lithium Enalates" 有機合成化学協会誌. 53. 1021-1032 (1995)
[Publications] Maki Uragami: "Highly Enantioselective Aldol Roaction Mediated by Mrted Aggregates Derned from a Lithium Ester Enolate and Tetradentate Chiral Lithium Awide" Tetrahedion:Asymmetry. 6. 701-704 (1995)
[Publications] Toshiya TAKAHASHI: "Enantioselective Darsens Reaction:Asymmetric Synthesrs of trans- Glycidic Ester Mediated by Chirol Lithium Amides" Chem.Pharm.Bull.43. 1821-1823 (1995)
[Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates:Novel Chiral Proton Sources and Remarkable Effects of the Countercation" J.Org.Chem.60. 1914-1915 (1995)
[Publications] Kaoru Fuji: "An Enantioselective Synthesrs of (-)-Pseudophrynaminol through Asymmetric Nitroolefination" Synlett.367-368 (1995)
[Publications] Fujie Tanaka: "1、1′-Binaphthalene-2、2′-diol as a Chirol Auxiliary.Diastereoselective Alkylation of Binaphthyl Esters,Complex-Jnluced Pnximity Ellects in Endate Formation.and One step Synthesrs of an Optically Active β-Substituted Roto" J.Am.Chem.Soc.117. 12159-12171 (1995)
[Publications] T.Mukaiyama: "An Efficient Glycosylation Reaction of 1-Hydroxy Sugars with Various Nucleophiles Using A Catalytic Amaunt of Activator and Heomethyldisiloxane" Stnthesis. 1368-1373 (1994)
[Publications] H.Uchiro: "Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hyclroxyvibofuranose" Chem.Lett.79-80 (1996)
[Publications] H-Uchiro: "A Signrticant Eflect of a Lithium Salt in the Steroocontrolled Syuthesrs of α-D-Ribofuranosicles" Chem-Lett.in press. (1996)
[Publications] Kiyoshi Tomioka: "Diastereoselective Throphenol Addition to (S)-N-α、β-Unsaturated Carbonyl-r-trrtyloxymethyl-r-butyrolactams" J.Org.Chem.60. 6188-6190 (1995)
[Publications] Motomu Kanai: "Asymmetric Conjugate Additron of Organomagnesium Caprates Controlled by Stoichiometric Ameunt of Chiral Phosphine" Tetrahedron letters. 36. 4273-4274 (1995)
[Publications] Motomu Kanai: "Catalytic Asymmetric Conjugate Additron of Grignard Reagents Contolled by Copper(I)-Chiral Bidentate Phosphine Complex." Tetrahedron letters. 36. 4275-4278 (1995)
[Publications] E.Nakamuia: "Selectivities Carbometalation of Olefins.Experimental Results and Theovetical Analysrs" Pure Appl Chem.68. 123-130 (1996)
[Publications] S.Mori: "Theoretical Studies no Chelation Controlled Carboryl Additron.Ml2Mg Addition to α-and β-Alkory Ketones and Aldehyces" J.Am.Chem.Soc.117. 5055-5065 (1995)
[Publications] S.Yamago: "Tertiary Phosphines,P-Chiral Phosphinites and Phosphonic Acid Esters Bearing Fullerene Substituant.Metol Complexes and Redox Proporbes" Tetrahedron. in press.

1995 Fiscal Year Annual Research Report

不斉空間の構築

Principal Investigator

古賀 憲司 東京大学, 薬学部, 教授 (10012600)

Research Products

[Publications] Kenji Koga: "Approaches to Catalytic Asymmetic Formation and Reactions of Lithium Enalates" 有機合成化学協会誌. 53. 1021-1032 (1995)

[Publications] Maki Uragami: "Highly Enantioselective Aldol Roaction Mediated by Mrted Aggregates Derned from a Lithium Ester Enolate and Tetradentate Chiral Lithium Awide" Tetrahedion:Asymmetry. 6. 701-704 (1995)

[Publications] Toshiya TAKAHASHI: "Enantioselective Darsens Reaction:Asymmetric Synthesrs of trans- Glycidic Ester Mediated by Chirol Lithium Amides" Chem.Pharm.Bull.43. 1821-1823 (1995)

[Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates:Novel Chiral Proton Sources and Remarkable Effects of the Countercation" J.Org.Chem.60. 1914-1915 (1995)

[Publications] Kaoru Fuji: "An Enantioselective Synthesrs of (-)-Pseudophrynaminol through Asymmetric Nitroolefination" Synlett.367-368 (1995)

[Publications] Fujie Tanaka: "1、1′-Binaphthalene-2、2′-diol as a Chirol Auxiliary.Diastereoselective Alkylation of Binaphthyl Esters,Complex-Jnluced Pnximity Ellects in Endate Formation.and One step Synthesrs of an Optically Active β-Substituted Roto" J.Am.Chem.Soc.117. 12159-12171 (1995)

[Publications] T.Mukaiyama: "An Efficient Glycosylation Reaction of 1-Hydroxy Sugars with Various Nucleophiles Using A Catalytic Amaunt of Activator and Heomethyldisiloxane" Stnthesis. 1368-1373 (1994)

[Publications] H.Uchiro: "Trityl Salt Catalyzed Stereoselective Glycosylation of Alcohols with 1-Hyclroxyvibofuranose" Chem.Lett.79-80 (1996)

[Publications] H-Uchiro: "A Signrticant Eflect of a Lithium Salt in the Steroocontrolled Syuthesrs of α-D-Ribofuranosicles" Chem-Lett.in press. (1996)

[Publications] Kiyoshi Tomioka: "Diastereoselective Throphenol Addition to (S)-N-α、β-Unsaturated Carbonyl-r-trrtyloxymethyl-r-butyrolactams" J.Org.Chem.60. 6188-6190 (1995)

[Publications] Motomu Kanai: "Asymmetric Conjugate Additron of Organomagnesium Caprates Controlled by Stoichiometric Ameunt of Chiral Phosphine" Tetrahedron letters. 36. 4273-4274 (1995)

[Publications] Motomu Kanai: "Catalytic Asymmetric Conjugate Additron of Grignard Reagents Contolled by Copper(I)-Chiral Bidentate Phosphine Complex." Tetrahedron letters. 36. 4275-4278 (1995)

[Publications] E.Nakamuia: "Selectivities Carbometalation of Olefins.Experimental Results and Theovetical Analysrs" Pure Appl Chem.68. 123-130 (1996)

[Publications] S.Mori: "Theoretical Studies no Chelation Controlled Carboryl Additron.Ml2Mg Addition to α-and β-Alkory Ketones and Aldehyces" J.Am.Chem.Soc.117. 5055-5065 (1995)

[Publications] S.Yamago: "Tertiary Phosphines,P-Chiral Phosphinites and Phosphonic Acid Esters Bearing Fullerene Substituant.Metol Complexes and Redox Proporbes" Tetrahedron. in press.

古賀憲司東京大学, 薬学部, 教授 (10012600)