Allylindation of Cyclopropenes Stereochemically Regulated by the Chelation

螯合立体化学调控环丙烯的烯丙基化

• 批准号: 10640518
• 负责人: ARAKI Shuki
• 金额: $ 2.37万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10640518/
• 关键词: Indium; Allylation; Cyclopropene; Cyclopropane; Chelation; Norbornenol; Stereoselectivity; Regioselectivity; ノルボルネン; 選択性; インジウム反応剤; 立体選択的合成

The chelation effects of a hydroxy group on the reactivities and selectivities have systematically been studied in the addition reactions of allylindium reagents (allylindation) to cyclopropenes and related compounds possessing a hydroxy group.The cyclopropenes bearing a hydroxy group in the 3-position chelate readily to allylindium reagents giving allylindation products highly regio- and stereoselectively. In the allylindation of the cyclopropenes with a hydroxyalkyl group at the 1-position, the selectivities depend largely on the length of the hydroxyalkyl chain. Thus, the selectivities are found to be switched by the location of the hydroxy group. Further, changing the allylindium reagents and the reaction solvents nicely regulated the selectivities. The structure of the allylindation product, cyclopropylindium, has fully been characterized by X-ray crystallography.Norbornenol derivatives possessing a strained carbon-carbon double bond also underwent clean allylindation, where the hydroxy group accelerates the allylindation as well as controls high regio- and stereoselectivities.

本文系统地研究了烯丙基试剂（烯丙基化）与环丙烯及含羟基化合物加成反应中羟基对反应活性和选择性的螯合作用。在3位上带有羟基的环丙烯很容易与烯丙基试剂螯合，使烯丙基化产物具有高度的区域选择性和立体选择性。在环丙烯与1位羟基烷基的烯丙基化反应中，选择性很大程度上取决于羟基烷基链的长度。因此，发现选择性被羟基的位置所改变。此外，改变烯丙lindium试剂和反应溶剂可以很好地调节选择性。烯丙基化产物环丙基的结构已经用x射线晶体学进行了全面表征。具有张力碳碳双键的降冰片烯醇衍生物也经历了干净的烯丙基化，其中羟基加速了烯丙基化，并控制了高的区域选择性和立体选择性。

项目成果

S.Araki 他7名: "Allylindation of Cyclopropenes in Organic and Aqueous Media. Switching the Regio- and Stereoselectivity Based on the Chelation with a Hydroxy Group and the Crystal Structure of the Cyclopropylindium Product"Chemistry-A European Journal. (印刷中

S.Araki 和其他 7 人：“环丙烯在有机和水介质中的烯丙基化。根据与羟基的螯合和环丙基铟产品的晶体结构切换区域和立体选择性”化学-欧洲杂志（出版中）。

S.Araki et al.: "Chelation-controlled Regio- and Stereoselective Allylindation of Norbornenols"Tetrahedron Letters. 40. 7999-8002 (1999)

S.Araki等人：“螯合控制的降冰片烯醇的区域和立体选择性烯丙基化”四面体字母。

S.Araki et al.: "Allylindation of Cyclopropenes in Organic and Aqueous Media. Switching the Regio- and Stereoselectivity Based on the Chelation with a Hydroxy Group and the Crystal Structure of the Cyclopropylindium Product"Chemistry-A European Journal. (

S.Araki等人：“环丙烯在有机和水介质中的烯丙基化。基于与羟基的螯合和环丙基铟产物的晶体结构切换区域选择性和立体选择性”化学-欧洲杂志。

S.Araki 他5名: "Chelation-controlled Regio-and Stereoselective Allylindation of Norbornenols"Tetrahedron Letters. 40. 7999-8002 (1999)

S. Araki 等人 5：“降冰片烯醇的螯合控制区域选择性烯丙基化”四面体快报 40. 7999-8002 (1999)