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.

最近，外消旋仲醇和内消旋二醇的非酶促不对称酰化受到了广泛关注，我们还通过与非手性苯甲酰卤存在下的反应证明了外消旋仲醇和内消旋1,2-二醇的不对称酰化。一些基于醇与非手性酰化剂的催化不对称酰化的论文已经出现。然而，这两种方法都没有发展到在有机合成中广泛应用的水平。我们确定衍生自 (S)-脯氨酸的手性二胺可以作为催化不对称化的高效催化剂。 mesa-1,2-二醇的催化不对称酰化已通过与苯甲酰氯在0.5 mol%存在下成功进行。手性二胺与化学计量的三乙胺结合，得到具有良好至优异对映选择性的相应单苯甲酸酯。在仅 0.3 moL% 的手性二胺存在下，也可以使用非手性苯甲酰氯成功地进行外消旋仲醇的催化不对称酰化。 (S)-脯氨酸，与0.5当量的三乙胺结合。醇与在-78℃下，在 TMEDA 存在下，苯甲酰氯发生非常快速的酰化反应，以优异的收率得到相应的苯甲酸酯。

项目成果

T.Oriyama, K.Imai, T.Hosoya, and T.Sano: "Asymmetric Acylation of meso-Diols with Benzoyl Halide in the Presence of a Chiral Diamine" Tetrahedron Lett.39. 397-400 (1998)

T.Oriyama、K.Imai、T.Hosoya 和 T.Sano：“手性二胺存在下内消旋二醇与苯甲酰卤的不对称酰化”四面体 Lett.39。

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。