1998 Fiscal Year Annual Research Report

炭素-ヘテロ原子二重結合の錯体触媒を用いた不斉水素化

Research Project

Project/Area Number	10125222
Research Institution	Osaka University
Principal Investigator	谷一英大阪大学, 大学院・基礎工学研究科, 教授 (60029444)
Co-Investigator(Kenkyū-buntansha)	山縣恒明大阪大学, 大学院・基礎工学研究科, 助手 (70166594) 片岡靖隆大阪大学, 大学院・基礎工学研究科, 助手 (90221879)
Keywords	イリジウム / BINAP / O-H活性化 / ペンジルアミン / カルボン酸 / プロトン性化合物 / オルトメタル化 / カチオン性錯体
Research Abstract	1. 我々は、イリジウム(I)-BINAP(2,2'-ビス(ジフェニルホスフィノ)-1.1'-ピナフチル)-1級または2級アミンからなる触媒系がメタノール中イミンの不斉水素化に効果的であることを見いだしている。この触媒反応の反応機構解明のため、触媒系の前駆体である、[IrCl(binap)]_2と種々のプロトン性化合物との反応を検討した。その結果、メタノール、水、カルボン酸、チオールのO-H結合あるいはS-H結合が活性化され、イリジウムに酸化敵付加したカチオン性のヒドリド(メトキソ)、ヒドリド(ヒドロキソ)、ヒドリド(カルボキシラート)、およびヒドリド(チオラート)二核イリジウム(I)錯体が高取率で得られた。 2. [IrCl(binap)]_2と触媒系の添加剤である1級ベンジルアミンおよび、その誘導体との反応を検討した。[IrCl(binap)]_2とベンジルアミン誘導体を、トルエン溶媒中70℃で3時間反応させると、オルトメタル化したヒドリドアリール錯体のジアステレオマー混合物が、白色粉末として定量的に得られた。その構造を^1Hおよび^<31>P{^1H}NMRスペクトル、2次元COSYおよびNOESYを用いて明らかにした。 3. ヒドリド(カルボキシラート)イリジウム(I)錯体を用いると、6員環環状イミンの不斉水素化において最高93%代の高い光学収率で対応するアミンが得られた.この錯体を用いると従来必要であった活性な触媒系創出のための前処理が必要でなくなる。また、アミンを添加しなくても高収率、高選択的に水素化反応が進行するので、生成物であるアミンを簡便に単離することができた。また、この触媒系は基質に対する特異性が高く、目的の炭素ー窒素二重結合のみを選択的に還元することができる.

Research Products

(13 results)

All Other

All Publications (13 results)

[Publications] 真島和志: "Theoretical Stufies of Multiple Meteal-Metal Bonds between Divalent Molybdenum Ions in Dimers, Tetramera, and Clusters" Bull.Chem.Soc.Jpn.71. 99-112 (1998)
[Publications] 真島和志: "1,8-Diphenylocta-1,3,5,7-tetraene Complexes of Ruthenium(II) : Crystal Structures of [μ-(s-cis-1,2,3,4-η ; S-cis-5,6,7,8-η-PhCH=CHCH=CHCH=CH-CH=CHPh)(RuClCp^*)2] and [μ-(s-trans-1,2,3,4-η ; s-trans-5,6,7,8-η-PhCH=CHCH=CHCH=CHCH=CHPh) {Ru(acac)2}2]" Organometallics. 17. 410-414 (1998)
[Publications] 真島和志: "Unique Complexation by the Tridentate Ligands, 6-Diphenylphosphino-2-pyridonate (pyphos) and 6-Diphenylphosphino-2-pyridone (pyphosH), on Ruthenium(II): Crystal Structures of (pyphosH) RuCl(μ-Cl)Mo_2Cl(Pyphos)_3, RuCl-(CO)(pyphosH)_2,[Ru(pyphos)_3] (μ-Na)_2[Ru(Ryphos)_3" Inorganica Chimica Acta (Bioinorg. Chem.). 270. 459-466 (1998)
[Publications] 谷一英: "Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh(binap)-(MeOH)_2]ClO_4 in Methanol" J.Organomet. Chem.560. 253-255 (1998)
[Publications] 真島和志: "Polymerization of methyl methacrylate eatalyzed by tantalum-diene complexes, Ta(η^5-C_5R_5)(η^4-l,3-butadiene)_2 (R=H and Me), in the presence of cocatalyst AlMe(OC_6H_2-2,6-(^tBu)_2-4-Me)_2" Proc.Japan Acad.74,SerB. 217-220 (1998)
[Publications] 片岡靖隆: "Highl Diastereoselectiv Oxidative Addition of Alkyl Halides to Rhodium and Iridium Carbonyl Complexes Having an η^5 : η^1-(Ind-P)_n Ligand((Ind-P)_n H=C_9H_7-(CH_2) PR_2 ; R=Ph,Cy ; n=2-4)" Organometallics. 17. 4338-4340 (1998)
[Publications] 押木俊之: "Oxidative Addition of a Hypervalent Transannular Sulfur-Sulfur Bond to a Pd(O) Complex : synthesis and Crystal Structures of 1,5-Dithiacyclooctanepalladium(II) Bis(trifluoromethanesulfonate) Having Phosphine Ligands" Bull.Chem.Soc.Jpn.71. 2859-2864 (1998)
[Publications] 真島和志: "The First Oxidative Addition of a Hypervalent Compound to Metallic Lanthanoid : Synthesis. Characterization, and Reaction of Samarium(II) Bis(trifluoromethane-sulfonate) Derived from Metallic Samarium and 1,5-Dithiabicyclo[3.3.0]octane Bis(trifluoromethanesulfonate)" J.Org.Chem.63. 7114-7116 (1998)
[Publications] 真島和志: "Asymmetric Transfer Hydrogenation of Ketonic Substrates catalyzed by (η^5-C_5Me_5)MCl Complexes (M=Rh and Ir) of (1S,2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine" Chem.Lett.1199-1200 (1998)
[Publications] 真島和志: "The Half-sandwich Hydride and 16-Electron complexes of Rhodium and Iridium Containing (1S,2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine : Relevant to the Asymmetric Transfer Hydrogenation" Chem.Lett.1201-1202 (1998)
[Publications] 谷一英: "Facile Oxidativ Addition of O-H Bonds of Methanol and Water to Ir^l Complexes Having Peraryldiphoshine Ligands ; Isolation and Characterization of Hydrido(methoxo)-and Hydrido(hydroxo)complexes of Ir^<III>" Angew.Chem.Int.Ed.37. 3381-3383 (1998)
[Publications] 真島和志: "Dative Pd(O) - Mo(II) Bonds in a Linearly Aligned Tetrametal System: Preparation, Characterization, and Reaction of a Tetranuclear Pd(O)-Mo(II)-Mo(II)-Pd(O) Supported by Four 6-Diphenylphosphino-2-pyridonate Ligands" J.Am.Chem.Soc.120. 12151-12152 (1998)
[Publications] 谷一英: "Isomerization of Olefin and the Related Reactions" Transition Metals for Organic Synthesis : Building Blocks and Fine Chemicals ed. by M. Beller and C. Bolm, Vol 1, Chapter 2.9,pp147-157, Wiley-VCH,Weinheim, 1998, 10 (1998)

1998 Fiscal Year Annual Research Report

炭素-ヘテロ原子二重結合の錯体触媒を用いた不斉水素化

Principal Investigator

谷 一英 大阪大学, 大学院・基礎工学研究科, 教授 (60029444)

Research Products

[Publications] 真島和志: "Theoretical Stufies of Multiple Meteal-Metal Bonds between Divalent Molybdenum Ions in Dimers, Tetramera, and Clusters" Bull.Chem.Soc.Jpn.71. 99-112 (1998)

[Publications] 谷 一英: "Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh(binap)-(MeOH)_2]ClO_4 in Methanol" J.Organomet. Chem.560. 253-255 (1998)

[Publications] 真島和志: "Polymerization of methyl methacrylate eatalyzed by tantalum-diene complexes, Ta(η^5-C_5R_5)(η^4-l,3-butadiene)_2 (R=H and Me), in the presence of cocatalyst AlMe(OC_6H_2-2,6-(^tBu)_2-4-Me)_2" Proc.Japan Acad.74,SerB. 217-220 (1998)

[Publications] 片岡靖隆: "Highl Diastereoselectiv Oxidative Addition of Alkyl Halides to Rhodium and Iridium Carbonyl Complexes Having an η^5 : η^1-(Ind-P)_n Ligand((Ind-P)_n H=C_9H_7-(CH_2) PR_2 ; R=Ph,Cy ; n=2-4)" Organometallics. 17. 4338-4340 (1998)

[Publications] 押木俊之: "Oxidative Addition of a Hypervalent Transannular Sulfur-Sulfur Bond to a Pd(O) Complex : synthesis and Crystal Structures of 1,5-Dithiacyclooctanepalladium(II) Bis(trifluoromethanesulfonate) Having Phosphine Ligands" Bull.Chem.Soc.Jpn.71. 2859-2864 (1998)

[Publications] 真島和志: "Asymmetric Transfer Hydrogenation of Ketonic Substrates catalyzed by (η^5-C_5Me_5)MCl Complexes (M=Rh and Ir) of (1S,2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine" Chem.Lett.1199-1200 (1998)

[Publications] 真島和志: "The Half-sandwich Hydride and 16-Electron complexes of Rhodium and Iridium Containing (1S,2S)-N-(p-Toluenesulfonyl)-1,2-diphenylethylenediamine : Relevant to the Asymmetric Transfer Hydrogenation" Chem.Lett.1201-1202 (1998)

[Publications] 谷 一英: "Facile Oxidativ Addition of O-H Bonds of Methanol and Water to Ir^l Complexes Having Peraryldiphoshine Ligands ; Isolation and Characterization of Hydrido(methoxo)-and Hydrido(hydroxo)complexes of Ir^<III>" Angew.Chem.Int.Ed.37. 3381-3383 (1998)

[Publications] 真島和志: "Dative Pd(O) - Mo(II) Bonds in a Linearly Aligned Tetrametal System: Preparation, Characterization, and Reaction of a Tetranuclear Pd(O)-Mo(II)-Mo(II)-Pd(O) Supported by Four 6-Diphenylphosphino-2-pyridonate Ligands" J.Am.Chem.Soc.120. 12151-12152 (1998)

[Publications] 谷 一英: "Isomerization of Olefin and the Related Reactions" Transition Metals for Organic Synthesis : Building Blocks and Fine Chemicals ed. by M. Beller and C. Bolm, Vol 1, Chapter 2.9,pp147-157, Wiley-VCH,Weinheim, 1998, 10 (1998)

谷一英大阪大学, 大学院・基礎工学研究科, 教授 (60029444)

[Publications] 谷一英: "Reductive dimerization of dialkyl acetylenedicarboxylate catalyzed by [Rh(binap)-(MeOH)_2]ClO_4 in Methanol" J.Organomet. Chem.560. 253-255 (1998)

[Publications] 谷一英: "Facile Oxidativ Addition of O-H Bonds of Methanol and Water to Ir^l Complexes Having Peraryldiphoshine Ligands ; Isolation and Characterization of Hydrido(methoxo)-and Hydrido(hydroxo)complexes of Ir^<III>" Angew.Chem.Int.Ed.37. 3381-3383 (1998)

[Publications] 谷一英: "Isomerization of Olefin and the Related Reactions" Transition Metals for Organic Synthesis : Building Blocks and Fine Chemicals ed. by M. Beller and C. Bolm, Vol 1, Chapter 2.9,pp147-157, Wiley-VCH,Weinheim, 1998, 10 (1998)