A Stereocontrolled Nucleophilic Addition to Imines and a Catalytic Asymmetric Reaction

亚胺的立体控制亲核加成和催化不对称反应

• 批准号: 06651010
• 负责人: WADA Makoto
• 金额: $ 0.26万
• 依托单位: Tokushima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06651010/
• 关键词: beta-Amino alcohol; alpha-Siloxy aldimine; Imine; Allylation; Diastereoselectivity; Cyanation; alpha-Amino nitrile; Bismuth compound; 立体化学制御; 求核的付加反応

A stereocontrolled nucleophilic addition to imines and a catalytic asymmetric reaction are described as follows.1. When alpha-siloxy aldimines were allowed to react with RLi followed by hydrolysis of the siloxy compounds, threo beta-amino alcohols were obtained stereoselectively. However, to our great suprise, the reaction of alpha-siloxy aldimines with RCu・BF_3 afforded erythro compounds exclusively.2. Allylic bromides reacted with imines at 60ﾟC in acetonitrile to give the corresponding homoallylamines in good yields in the presence of bismuth trichloride-metallic zine. Diastereoselectivity of the present reaction was investigated by using crotyl bromide-imines or optically active imines-allyl bromide.3. It was found that imines reacted with trimethylsilyl cyanide in the presence of a catalytic amount of bismuth trichloride to afford alpha-amino nitriles in good yields. Enantionselective cyanation of imines took place by using asymmetric bismuth compound prepared from optically active ethyl tartrate.

本文介绍了亚胺的立体控制亲核加成和催化不对称反应。当α-甲硅烷氧基醛亚胺与RLi反应，然后水解甲硅烷氧基化合物时，立体选择性地得到苏式β-氨基醇。然而，令人惊讶的是，α-甲硅烷氧基醛亚胺与RCu·BF_3的反应只生成了邻位化合物.在三氯化铋-金属锌存在下，烯丙基溴与亚胺在乙腈中于60 ℃反应，高产率地得到相应的高烯丙基胺。以巴豆酰溴-亚胺或光学活性亚胺-烯丙基溴为原料，研究了该反应的非对映选择性.研究发现，在催化量的铋存在下，亚胺与三甲基硅腈反应，以良好的产率得到α-氨基腈。用光学活性酒石酸乙酯制备的不对称铋化合物对亚胺进行了不对称氰化反应。

项目成果

Makoto Wada,Norikazu Miyoshi,Masashi Matsuzaki,and Tokunaru Horie: "A Grignard-Type Addition of Allyl Unit to Imines by Using Bismuth Trichloride-Metallic Zinc" Manuscript in preparation in Chem.Lett.

Makoto Wada、Norikazu Miyoshi、Masashi Matsuzaki 和 Tokunaru Horie：“使用三氯化铋-金属锌对亚胺进行格氏加成烯丙基单元”手稿正在 Chem.Lett 中准备。

Makoto Wada, Norikazu Miyoshi, Masashi Matsuzaki, and Tokunaru Horie: "A Grignard-Type Addition of Allyl Unit to Imines by Using Bismuth Trichloride-Metallic Zinc" Manuscript in preparation in Chem. Lett.

Makoto Wada、Norikazu Miyoshi、Masashi Matsuzaki 和 Tokunaru Horie：“使用三氯化铋-金属锌对亚胺进行格氏加成烯丙基单元”手稿正在 Chem 中准备。

Makoto Wada,Norikazu Miyoshi,Masashi Matsuzaki,and Tokunaru Horie: "Bismuth Mediated Cyanation of Imines by Using Trimethylsilyl Cyanide" Manuscript in preparation in Chem.Lett.

Makoto Wada、Norikazu Miyoshi、Masashi Matsuzaki 和 Tokunaru Horie：“使用三甲基甲硅烷基氰化物对亚胺进行铋介导的氰化”手稿正在 Chem.Lett 中准备。

Makoto Wada, Norikazu Miyoshi, Masashi Matsuzaki, and Tokunaru Horie: "A Grignard-Type Addition of Allyl Unit to Imines by Using Bismuth Trichloride-Metallic Zinc" Manuscript in Preparation in Chen.

Makoto Wada、Norikazu Miyoshi、Masashi Matsuzaki 和 Tokunaru Horie：“使用三氯化铋-金属锌对亚胺进行格氏加成烯丙基单元”手稿正在准备中，陈。

Makoto Wada, Norikazu Miyoshi, Masashi Matsuzaki, and Tokunaru Horie: "Bismuth Mediated Cyanation of Imines by Using Trimethylsilyl Cyanide" Manuscript in preparation in Chen.

Makoto Wada、Norikazu Miyoshi、Masashi Matsuzaki 和 Tokunaru Horie：“使用三甲基甲硅烷基氰化物对亚胺进行铋介导的氰化”手稿正在准备中，Chen。