Nonenzymatic Asymmetric Acylation of meso-Diols

内消旋二醇的非酶促不对称酰化

• 批准号: 09640705
• 负责人: ORIYAMA Takeshi
• 金额: $ 1.86万
• 依托单位: IBARAKI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640705/
• 关键词: meso-diol; chiral diamine; benzoyl chloride; racemic secondary alcohol; triethylamine; asymmetrization; kinetic resolution; catalytic asymmetric acylation; 対称-1,2-ジオール; 光学活性ジアミン

Recently, much attention has been focused on the nonenzymatic asymmetric acylation of racemic secondary alcohols and meso-diols. We have also demonstrated asymmetric acylation of racemic secondary alcohols and meso-1,2-diols by the reaction with achiral benzoyl halide in the presence of a chiral diamine derived from (S)-proline. Some papers which are based on the catalytic asymmetric acylation of alcohols with achiral acylating agents have emerged successively in recent years. However, neither methodology has been developed to such a level as to find widespread use in organic synthesis.We establish that a chiral diamine derived from (S)-proline can function as a highly efficient catalyst for the catalytic asymmetrization of meso-1 , 2-diols. Catalytic asymmetric acylation of mesa-1,2-diols has been successfully performed by the reaction with benzoyl chloride in the presence of 0.5 mol% of chiral diamine combined with a stoichiometric amount of triethylamine to give the corresponding monobenzoate with good to excellent enantioselectivities. Catalytic asymmetric acylation of racemic secondary alcohols has been also successfully performed with achiral benzoyl chloride in the presence of only 0.3 moL% of chiral diamine derived from (S)-proline, combined with 0.5 equivalent of triethylamine.Reactions of alcohols with benzoyl chloride in the presence of TMEDA at -78 ﾟC resulted in very fast acylation to afford the corresponding benzoates in excellent yields.

近年来，外消旋仲醇和内消旋二醇的非酶不对称酰化反应受到了广泛的关注。我们还证明了外消旋仲醇和meso-1，2-二醇的不对称酰化反应与非手性苯甲酰卤在存在下衍生自（S）-脯氨酸的手性二胺。近年来，以非手性酰化剂催化的醇的不对称酰化反应为基础的研究成果不断涌现。然而，这两种方法都没有发展到这样的水平，以发现在有机合成中广泛使用。我们建立了一个手性二胺衍生自（S）-脯氨酸可以作为一个高效的催化剂的催化不对称的meso-1，2-diols。在0.5mol%的手性二胺和化学计量的三乙胺存在下，mesa-1，2-二醇与苯甲酰氯反应，成功地催化了mesa-1，2-二醇的不对称酰化反应，得到了具有良好对映选择性的单苯甲酸酯。在0.3 moL%的（S）-脯氨酸衍生的手性二胺和0.5当量的三乙胺的存在下，外消旋仲醇与苯甲酰氯的催化不对称酰化反应也已成功地进行，醇与苯甲酰氯在TMEDA存在下于-78 ℃下的酰化反应非常快，以优异的产率得到相应的苯甲酸酯。

项目成果

T.Sano, K.Imai K.Ohashi, and T.Oriyama: "Catalytic Asymmetric Acylation of Racemic Secondary Alcohols with Beugoyl Chloride in the Presence of a Chiral Diamine" Chem.Lett.265-266 (1999)

T.Sano、K.Imai K.Ohashi 和 T.Oriyama：“在手性二胺存在下，外消旋仲醇与 Beugoyl Chloride 的催化不对称酰化” Chem.Lett.265-266 (1999)

T.Oriyama, K.Imai, T.Sano, and T.Hosoya: "Highly Efficient Catalytic Asymmetric Acylation of meso-1,2-Diols with Benzoyl Chloride in the Presence of a Chiral Diamine Combined with Et_3N" Tetrahedron Lett.(in press).

T.Oriyama、K.Imai、T.Sano 和 T.Hosoya：“在手性二胺与 Et_3N 存在下，高效催化内消旋 1,2-二醇与苯甲酰氯的不对称酰化”四面体快报。（in

T.Sano, K.Ohashi, and T.Oriyama: "Remarkably Fast Acylation of Alichels with Benyoyl Chloride Promoted by TMEDA" Synthesis. in press.

T.Sano、K.Ohashi 和 T.Oriyama：“TMEDA 促进的苯甲酰氯对 Alichels 进行非常快速的酰化”合成。

T.Oriyama, K.Imai, T.Sano, and T.Hosoya: "Highly Efficient Catalytic Asymmetric Acylation of meso-1,2-Diols with Benzoyl Chloride in the Presence of a Chiral Diamine Combined with Et_3N" Tetrahedron Lett.39. 3529-3532 (1998)

T.Oriyama、K.Imai、T.Sano 和 T.Hosoya：“在与 Et_3N 结合的手性二胺存在下，内消旋 1,2-二醇与苯甲酰氯的高效催化不对称酰化”四面体 Lett.39。

T.Oriyama,K.Imai,T.Sano,and T.Hosoya: "Highly Efficient Catalytic Asymmetric Acylation of meso-1,2-Diols with Benzoyl Chloride in the Presence of a Chiral Diamine Combined with Et_3N" Tetrahedron Lett.39. 3529-3532 (1998)

T.Oriyama、K.Imai、T.Sano 和 T.Hosoya：“在与 Et_3N 结合的手性二胺存在下，内消旋 1,2-二醇与苯甲酰氯的高效催化不对称酰化”四面体 Lett.39。