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.

描述了通过手性辣椒剂催化的不对称环丙旋植物，环氧化和副氮化。由C2对称性手性甲状腺素轴承异位醇或樟脑骨骼形成的新型刘易斯酸/布朗斯特基碱催化剂很容易从（1s）-10-碳磺酸（1S） - 苯甲酸制备。 Di-exo-2-Hydroxy-10-甲基硒化和LIH促进了溴化苯乙烯与甲基乙烯基酮的反应，以提供最高50％EE的所需反式环丙烷。苯乙烯还催化了苯乙烯溴与n-苯二苯基苯甲酰苯胺的反应，以产生高达60％EE的CIS Aziridine。尽管从苯溴化物与芳族醛的反应中获得了黄氧烷地层的良好产量和中等的对映射性，但与脂肪醛醛的反应为良好的产率和较差的映射性提供了所需的环氧化物的反应。

项目成果

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

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