Generation of unstable carbanions by ligand exchange reaction of sultoxides and application to new synthetic method

亚硫酸盐配体交换反应生成不稳定碳负离子及其在新合成方法中的应用

• 批准号: 08672451
• 负责人: SATHO Tsuyoshi
• 金额: $ 1.41万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08672451/
• 关键词: sulfoxide; olefin; carboxylic acid; ligand exchange; carbanion; carbenoid; aziridinyllithiun; homologation

Development of new synthetic methods by the ligand exchange reaction of sulfoxides were investigated and several new interesting results were obtained ; those are as follows.1.The reaction of sulfinyl aziridines with t-BuLi resulted in formation of aziridinyllithium in good yields. The property and synthetic application to alpha-dialkylamino acid derivatives were studied.2.Oxiranyllithium having carbanion destabilizing group (alkyl groups) were abled to be generated by the ligand exchange reaction of sulfinyloxirans. Property and applications to new synthetic method of epoxides and alcohols including optically active form were developed.3.alpha-Halovinyl sulfoxides were found to react with Grignard reagents to give magnesium alkylidene carbenoids. A new synthetic method for tetra-substituted olefins was realized by this reaction.4.A new method for one-carbon homologation of methylesters was realized and the method was applied to one-carbon ring expansion of lactones and to a homologation of alpha, beta-unsaturated aldehydes.5.Sulfoxide version of Julia-Lythgou olefination was realized via the ligand exchange reaction of beta-mesyloxy sulfoxides.

本文研究了亚砜配体交换反应合成氮杂环丙烷锂的新方法，得到了如下结果：1.亚磺酰基氮杂环丙烷与叔丁基锂反应，以较高的产率合成了氮杂环丙烷锂。2.通过亚磺酰环氧乙烷的配体交换反应，合成了具有碳负离子不稳定基团（烷基）的环氧乙烷基锂。研究了α-卤代乙烯基亚砜与格氏试剂反应生成烷叉卡宾镁的新方法。4.实现了甲酯的一碳同系化反应，并将其应用于内酯的一碳扩环反应和α，β-不饱和内酯的同系化反应。5.通过β-甲磺酰氧基亚砜的配体交换反应实现了亚砜型Julia-Lythgou烯烃化反应。

项目成果

T.Satoh: "Generation of Aziridinyllithiums from sultinylaziridine by the Ligand Exchange Reaction of Sultoxides with ・・・" Tetrahedron Lett. 39. (1998)

T.Satoh：“通过亚磺酰基氮丙啶与···的配体交换反应生成氮丙啶基锂”，Tetrahedron Lett 39。（1998）

T.Satoh, K.Takano, H.Ota, H.Someya, K.Matsuda, M.Koyama: "Magnesium Alkylidene Carbenoids : Generation from 1-Halovinyl Sulfoxides with Grignard Reagents and the Studies on Their Property, Mechnism, and Some Synthetic Uses" Tetrahedron. (in preparation).

T.Satoh、K.Takano、H.Ota、H.Someya、K.Matsuda、M.Koyama：“亚烷基类胡萝卜素镁：用格氏试剂生成 1-卤乙烯基亚砜及其性质、机理和一些合成的研究

T.Satoh: "A Versastile Procedure for One-Corbon Homologation of Methylesters to Esters,Thioesters,Carboxylic Acid and・・・" Tetrahedron. 53. 7843-7854 (1997)

T. Satoh：“一种将甲酯与酯、硫酯、羧酸等同系的多功能程序”，Tetrahedron，53。7843-7854 (1997)

T.Satoh: "A New Development in Organic Synthesis with Sulfavidess Novel Synthetic Methods through the Ligand Exchane・・・" J.Syn.Org.Chem.Jpn.54. 481-489 (1996)

T.Satoh：“通过配体交换的硫化物新合成方法有机合成的新进展……”J.Syn.Org.Chem.Jpn.54 (1996)。

T.Satoh: "Sulfoxide Version of the Julia-Lythgoe Olefination" Synlett.

T.Satoh：“Julia-Lythgoe 烯化的亚硫酸盐版本”Synlett。