Development of Asymmetric Reactions Catalyzed by Bronsted Acid in Aqueous Media

水介质中布朗斯台德酸催化不对称反应的研究进展

• 批准号: 12640528
• 负责人: AKIYAMA Takahiko
• 金额: $ 2.37万
• 依托单位: Gakushuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640528/
• 关键词: Bronsted Acid; Mannich-type Reaction; β-Aminc Carbonyl Compounds; Diastereoselectivity; Schiff bases; Water; 立体選択性; ブレンステッド酸; β-アミノエステル; ケテンシリルアセタール; 水; ジアステレオ選択性; 不斉合成

We have found that Mannich-type reactions took place smoothly under the influence of Bronsted acid, typically aq. HBF_4, to afford the corresponding (β-amino carbonyl compounds in high yields in aqueous organic solvents. Furthermore, the HBF_4-catalyzed Mannich-type reaction took place smoothly in the presence of sodium dodecyl sulfate in water under organic solvent-free conditions. Aza-Diels Alder reactions in aqueous media have been successfully achieved. Anti and syn stereoselectivity on the HBF_4-catalyzed Mannich-type reaction of ketene silyl acetal derived from α-oxy esters with aldimines were investigated. Whereas use of ketene silyl acetal derived from aryl ester in aqueous 2-propanol gave anti β-amino-α-siloxy ester with excellent stereoselectivity, use of ketene silyl acetal derived from methyl ester in water in the presence of sodium dodecyl sulfate gave the syn isomer preferentially.

我们发现曼尼希型反应在布朗斯台德酸（通常是HBF_4水溶液）的影响下顺利发生，在水性有机溶剂中以高产率生成相应的（β-氨基羰基化合物）。此外，HBF_4催化的曼尼希型反应。在无有机溶剂的条件下，在十二烷基硫酸钠的存在下，在水介质中成功地实现了 Aza-Diels Alder 反应。研究了在 2-丙醇水溶液中使用芳基酯衍生的乙烯酮甲硅烷基缩醛与醛亚胺进行 HBF_4 催化的曼尼希型反应，得到反 β-氨基-α-甲硅烷氧基酯。具有优异的立体选择性，在钠存在下使用由甲酯在水中衍生的烯酮甲硅烷基缩醛十二烷基硫酸盐优先产生顺式异构体。

项目成果

H. Kagoshima, T. Okamura, and T. Akiyama: "The Asymmetric [3+2] Cycloaddition Reaction of Chiral Alkenyl Fischer Carbene Complexes with Imines: Synthesis of Optically Pure 2,5-Disubstituted-3-Pyrrolidinones"J. Am. Chem. Soc.. 123. 7182-7183 (2001)

H. Kagoshima、T. Okamura 和 T. Akiyama：“手性烯基费舍尔卡宾配合物与亚胺的不对称 [3 2] 环加成反应：光学纯 2,5-二取代-3-吡咯烷酮的合成”J。

T. Akiyama, M. Sugano, and H. Kagoshima: "Lewis Acid-Mediated [3+2] Cycloaddition of Allyltriisopropylsilane to N-Sulfonyl Aldimines"Tetrahedron Lett.. 42. 3889-3992 (2001)

T. Akiyama、M. Sugano 和 H. Kagoshima：“路易斯酸介导的 [3 2] 烯丙基三异丙基硅烷与 N-磺酰醛亚胺的环加成”Tetrahedron Lett.. 42. 3889-3992 (2001)

T.Akiyama, J.Takaya, H.Kagoshima: "Bronsted Acid Catalyzed Mannich-type Reactions in Aqueous Media"Advanced Synthesis & Catalysis. 343(印刷中). (2002)

T.Akiyama、J.Takaya、H.Kagoshima：“水介质中的布朗斯台德酸催化曼尼希型反应”高级合成与催化 343（印刷中）。

T.Akiyama, J.Takaya, H.Kagoshima: "Bronsted Acid Catalyzed Mannich-type Reactions in Aqueous Media"Advanced Synthesis & Catalysis. 343(印刷中). (2002)

T.Akiyama、J.Takaya、H.Kagoshima：“水介质中的布朗斯台德酸催化曼尼希型反应”高级合成与催化 343（印刷中）。

J. Takaya, H. Kagoshima, and T. Akiyama: "Mannich-type Reaction with Trifluoromethylated N,O-Hemiacetal; Facile Preparation of β-Amino-β-Trifluoromethyl Carbonyl Compounds"Org. Lett.. 2. 1577-1579 (2000)

J. Takaya、H. Kagoshima 和 T. Akiyama：“三氟甲基化 N,O-半缩醛的曼尼希型反应；β-氨基-β-三氟甲基羰基化合物的简便制备”Org. 2. 1577-1579 ( 2000）