Development of the Formation of Enolate Controlled by Acid-base Bifunctional Organochalcogenide Catalysts

酸碱双功能有机硫属化物催化剂控制烯醇化生成的研究进展

• 批准号: 20590021
• 负责人: WATANABE Shinichi
• 金额: $ 3.08万
• 依托单位: Kinjo Gakuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20590021/
• 关键词: 不斉反応; 光学活性スルフィド; 光学活性セレニド; 光学活性テルリド; オキシラン; シクロプロパン; アジリジン; セレノニウム塩; 光学活性テルラン; 不斉触媒; 不斉シクロプロパン化; 不斉アジリジン化; ヘテロ原子化学; 合成化学; セレニド; ホスフィン; ジアステレオ選択性; スルフィド

Asymmetric cyclopropanation, epoxidation and aziridination catalyzed by chiral chalcogenides are described. A novel Lewis acid/Bronsted base catalysts formed by a C2 symmetric chiral chalcogenide bearing isoborneol or camphor skeletons were readily prepared from (1S)-10-camphorsulfonic acid. Di-exo-2-hydroxy-10- bornyl selenide and LiH promoted the reaction of phenacyl bromide with methyl vinyl ketone to afford the desired trans cyclopropane with up to 50% ee. The reaction of phenacyl bromide with N-benzylidene-4-methylbenzenesulfonamide was also catalyzed by the selenide to produce the cis aziridine with up to 60% ee. Although the good yields and moderate enantioselectivities for oxirane formations were obtained from the reaction of phenacyl bromide with aromatic aldehydes, the reactions with aliphatic aldehydes afforded the desired epoxides in good yields and poor enantioselectivities.

介绍了手性硫族化合物催化的不对称环丙烷化、环氧化和氮杂环丙烷化反应。以（1 S）-10-异冰片磺酸为原料，合成了一种由C2对称的手性硫属化合物构成的新型刘易斯酸/Bronsted碱催化剂。二-外-2-羟基-10-乙酰基硒醚和LiH促进苯甲酰甲基溴与甲基乙烯基酮反应生成反式环丙烷，ee值高达50%;苯甲酰甲基溴与N-亚苄基-4-甲基苯磺酰胺反应生成顺式氮丙啶，ee值高达60% ee.虽然苯甲酰甲基溴与芳香醛反应得到了良好的产率和中等的环氧乙烷形成对映选择性，与脂族醛的反应以良好的产率和差的对映选择性得到所需的环氧化物。

项目成果

Enantioselective Darzens reaction by chiral selenide catalysts

手性硒化物催化剂的对映选择性 Darzens 反应

• 发表时间: 2010
• 作者: Watanabe;Shin-ichi ; et al.;Watanabe Shin-ichi
• 通讯作者: Watanabe Shin-ichi

Enantioselective Darzens reaction using organoselenide-lithium hydroxide complexes

• DOI: 10.1016/j.tetlet.2010.08.082
• 发表时间: 2010-11
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Shin‐ichi Watanabe;Risa Hasebe;Junichi Ouchi;H. Nagasawa;T. Kataoka