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

α三氟甲基化烯醇化物的生成及其在不对称羟醛合成中的应用

• 批准号: 14550808
• 负责人: ISHIHARA Takashi
• 金额: $ 2.18万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550808/
• 关键词: 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

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.

当N-甲氧基-N-甲基-2-溴-2,3,3,3-四氟丙酰胺在三苯基膦和催化量的异丙醇钛(IV)的作用下在二氯甲烷中于室温下与各种醛反应时， (三氟甲基)-β-羟基酰胺优先以良好至优异的产率进行。此外，苄基的反应2-溴-2,3,3,3-四氟丙酸酯与各种类型的手性亚胺，例如(S)-亚磺亚胺和衍生自(S)-缬氨酸甲酯或(S)-苯基甘氨酸甲酯的亚胺，室温下四氢呋喃中锌的存在可提供苏式和赤式异构体α-氟-α-（三氟甲基）-β-氨基酯具有高非对映异构体过量，化学产率相当至良好。

项目成果

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

K.Sato、T.Sekiguchi、T.Ishihara、T.Konno、H.Yamanaka：“2-溴-2,3,3,3-四氟丙酰胺与醛的高度立体选择性羟醛型反应，生成赤式-α-氟-α-(三氟甲基)-β-羟基酰胺”《化学快报》第 33 卷第 2 期第 154 期

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"Chemist

T.Sekiguchi、K.Sato、T.Ishihara、T.Konno、H.Yamanaka：“锌介导的 2-溴-2,3,3,3-四氟丙酸酯与各种手性亚胺的偶联反应。简单有效地获得光学活性α-氟-α-(三氟甲基)-β-氨基酯”化学家

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)

T.Sekiguchi、K.Sato、T.Ishihara、T.Konno、H.Yamanaka：“锌介导的 2-溴-2,3,3,3-四氟丙酸酯的偶联反应获得光学活性 α-氟-α- (三氟甲基)-β-氨基酯”Chemistry Letters. 33 (No.6) (印刷中). (2004)

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. 1

K.Sato、T.Sekiguchi、T.Ishihara、T.Konno、H.Yamanaka：“2-溴-2,3,3,3-四氟丙烷酰胺与醛的高度立体选择性羟醛型反应导致赤式-α -氟-α-(三氟甲基)-β-羟基酰胺”Chemistry Letters. Vol.33, No.2. 1

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). 1

K.Sato、T.Sekiguchi、T.Ishihara、T.Konno、H.Yamanaka：“2-溴-2,3,3,3-四氟丙酰胺与醛的高度立体选择性羟醛型反应生成赤式-α-氟-α-(三氟甲基)-β-羟基酰胺”《化学快报》. 33 (No.2). 1