GENERATION OF αTRIFLUOROMETHYLATED ENOLATE SPECIES AND THEIR APPLICATION TO ASYMMETRIC ALDOL SYNTHESIS

• Project/Area Number: 14550808
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 有機工業化学
• Research Institution: Kyoto Institute of Technology
• Principal Investigator: ISHIHARA Takashi KYOTO INSTITUTE OF TECHNOLOGY, DEPARTMENT OF CHEMISTRY AND MATERIALS TECHNOLOGY, PROFESSOR, 工芸学部, 教授 (40093182)
• Project Period (FY): 2002 – 2003
• Project Status: Completed (Fiscal Year 2003)
• Budget Amount: ¥3,400,000 (Direct Cost: ¥3,400,000); Fiscal Year 2003: ¥1,100,000 (Direct Cost: ¥1,100,000); Fiscal Year 2002: ¥2,300,000 (Direct Cost: ¥2,300,000)
• Keywords: α-trifluoromethylated enolate species / fluorinated α-bromopropanoic acid derivatives / phosphine-lewis acid / asymmetric aldol-type reaction / reductive coupling reaction / erythro-selectivity / diastereoselectivity / 含フッ素α-ブロモプロパンアミド / 含フッ素2-オキサゾリジノンイミド / トリフルオロプロパン酸エステル / Reformatsky反応 / テトラフルオロプロパンアミド / ルイス酸触媒-トリフェニルホスフィン / 立体選択的アルドール反応 / α-トリフルオロメチル-β-ヒドロキシエステル / α-トリフルオロメチル-β-ヒドロキシアミド

Research Abstract

When N-methoxy-N-methyl-2-bromo-2, 3, 3, 3-tetrafluropropanamide was allowed to react with various aldehydes under the influence of triphenylphosphine and a catalytic amount of titanium (IV) isopropoxide in dichloromethane at room temperature, (trifluoromethyl)-β-hydroxy amides preferentially in good to excellent yields.
In addition, the reactions of benzyl 2-bromo-2, 3, 3, 3-tetrafluoropro-panoate with various types of chiral imines, such as (S)-sulfinimines and imines derived from (S)-valine methyl ester or (S)-phenylglycine methyl ester, in the presence of zinc in tetrahydrofuran at room temperature were revealed to afford the threo-and erythro-isomers of α-fluoro-α-(trifluoromethyl) -β-amino esters with high diasteremeric excesses in fair to good chemical yields.

Research Products

• [Publications] K.Sato, T.Sekiguchi, T.Ishihara, T.Konno, H.Yamanaka: "Highly Stereoselective Aldol-type Reaction of 2-Bromo-2,3,3,3-tetrafluoropropan-amide with Aldehydes Leading to erythro-α-Fluoro-α-(trifluoromethyl)-β-hydroxy Amides"Chemistry Letters. Vol.33, No.2. 154-155 (2004)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] T.Sekiguchi, K.Sato, T.Ishihara, T.Konno, H.Yamanaka: "Zinc-mediated Coupling Reaction of 2-Bromo-2,3,3,3-tetrafluoropropanoate with Various Chiral Imines. Simple and Effective Access to Optically Active α-Fluoro-α-(trifluoromethyl)-β-amino Esters"Chemistry Letters. Vol.33, No.6. (2004)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] K.Sato, T.Sekiguchi, T.Ishihara, T.Konno, H.Yamanaka: "Highly Stereoselective Aldol-type Reaction of 2-Bromo-2, 3, 3, 3-tetrafluoropropanamide with Aldehydes Leading to erythro-α-Fluoro-α-(trifluoromethyl) -β-hydroxy Amides"Chemistry Letters. 33 (No.2). 154-155 (2004)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] T.Sekiguchi, K.Sato, T.Ishihara, T.Konno, H.Yamanaka: "Zinc-mediated Coupling Reaction of 2-Bromo-2, 3, 3, 3-tetrafluoropropanoate Access to Optically Active α-Fluoro-α-(trifluoromethyl) -β-amino Esters"Chemistry Letters. 33 (No.6) (in press). (2004)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] K.Sato, T.Sekiguchi, T.Ishihara, T.Konno, H.Yamanaka: "Highly stereoselective aldol-type reaction of 2-bromo-2,3,3,3-tetrafluoropropanamide with aldehydes leading to erythro-α-fluoro-α-(trifluoromethyl)-β-hydroxy amides"Chemistry Letters. Vol.33,No.2. 154-155 (2004)