Exploration into Double Nucleophilic Addition Reaction to α, β- Unsaturated Aldimines Promoted by Titanium Tetrahalides

四卤化钛促进α,β-不饱和醛亚胺双亲核加成反应的探索

• 批准号: 12650833
• 负责人: SHIMIZU Makoto
• 金额: $ 2.05万
• 依托单位: Mie 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-12650833/
• 关键词: titanium tetrahalide; double nucleophilic addition; ketene silyl acetal; α,β-unsaturated aldimine; allylstannene; aluminum chloride; molecular sieves; thiol; 二重球核付加反応; 共役付加受容体; α-メタライミン

In the present study, we found that in the presence of a titanium tetrahalide, ketene silyl acetals underwent 1,4- and subsequently 1,2-addition to α, β-unsaturated aldimine to give doubly alkylated products in good yields. The reaction of a mixture of a ketene silyl acetal and an allyltributylstannane with α,β-unsaturated aldimine gave regio- and chemoselectively 1,4- and 1,2-doubly alkylated product, in which the ketene silyl acetal underwent 1,4-addition while the allyltributylstannane underwent 1,2-addition. Moreover, in the presence of AlCl_3 and MS 4A containing H_2O, ketene silyl acetals underwent 1,4- and then 1,2-addition with α,β-unsaturated imines to give doubly alkylated products in good yields with high diastereomeric excesses. A mixture of thiols and tetraallyltin also underwent 1,4- and 1,2-addition, respectively, with α, β-unsaturated imines with TiCl_4, to give 6-sulfenyl-4-amino-1-alkenes in good yields.

在本研究中，我们发现在四卤化钛存在下，烯酮甲硅烷基缩醛与α,β-不饱和醛亚胺进行1,4-加成，随后进行1,2-加成，以良好的收率得到双烷基化产物。乙烯酮甲硅烷基缩醛和烯丙基三丁基锡烷的混合物与α,β-不饱和醛亚胺反应，得到区域和化学选择性的1,4-和1,2-双烷基化产物，其中乙烯酮甲硅烷基缩醛进行1,4-加成，而烯丙基三丁基锡烷进行1,2-加成。此外，在AlCl_3和含有H_2O的MS 4A存在下，乙烯酮甲硅烷基缩醛与α,β-不饱和亚胺先进行1,4-加成，然后进行1,2-加成，以良好的收率和高非对映异构体过量得到双烷基化产物。硫醇和四烯丙锡的混合物也分别与α,β-不饱和亚胺和TiCl_4进行1,4-和1,2-加成，以良好的收率得到6-硫基-4-氨基-1-烯烃。

项目成果

M.Shimizu: "SChemoselective Deoxygenation of Sulfoxides with Titanium Tetraiodide"Synlett. (10). 1437-1438 (2000)

M.Shimizu：“用四碘化钛对亚砜进行化学选择性脱氧”Synlett。

M.Shimizu: "Reformatsky-type reaction of α-halo ketones promoted by titanium tetraiodide"Tetrahedron. 57,(47). 9591-9595 (2001)

M.Shimizu：“四碘化钛促进的 α-卤代酮的 Reformatsky 型反应”Tetrahedron 57，(47) (2001)。

M.Shimizu: "Retormatsky-type reaction of α-halo ketones promoted by titanium tetraiodide"Tetrahedron. 57,(47). 9591-9595 (2001)

M.Shimizu：“四碘化钛促进的 α-卤代酮的 Retormatsky 型反应”Tetrahedron 57，(47) (2001)。

M.Shimizu: "N-Alkylation-Coupling Reaction of Imines Promoted by Alkylaluminum Reagents, Leading to a Facile Synthesis of 1,2-Diamines"Tetrahedron Lett.. (in press). (2001)

M.Shimizu：“烷基铝试剂促进亚胺的 N-烷基化偶联反应，导致 1,2-二胺的简便合成”Tetrahedron Lett..（出版中）。

R.Hayakawa: "Reduction of 1,2-Diketones with Titanium Tetraiodide : A Simple Approach to α-Hydroxy Ketones"Tetrahedron Lett.. 41,(41). 7939-7942 (2000)

R.Hayakawa：“用四碘化钛还原 1,2-二酮：生成 α-羟基酮的简单方法”Tetrahedron Lett.. 41,(41) 7939-7942 (2000)。