Development of new synthetic reactions based on the reactions of α, β-epoxysilanes and nucleophiles

基于α，β-环氧硅烷和亲核试剂反应的新合成反应的开发

基本信息

批准号：
10671986
负责人：
TAKEDA Kei
金额：
$ 2.11万
依托单位：
Hiroshima University (2000)Toyama Medical and Pharmaceutical University (1998-1999)
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 2000
项目状态：
已结题

项目摘要

The objective of this study has been to develop new synthetic reactions based on the reaction of α, β-epoxysilanes with a nucleophile.1. Stereospecific Construction of Eight-Membered CarbocyclesWhen γ-acryloylacylsilane was treated with vinyllithium, a cyclooctenone derivative was obtained as a single diastereomer via an anionic oxy-Cope rearrangement of 1, 2-divinylcyclobutanediol intermediate generated by way of Brook rearrangement of the 1, 2-adduct of the vinyllithium. Furthermore, we found a more versatile methodology for the synthesis of the carbocycles, which involves the reaction of γ-vinyl-γ-silyl-γ-lactones, prepared from β-methoxycarbonyacylsilane with vinyllithium, with vinyllithium.2. Reaction of O-silyl Cyanohydrin derivatives of α, β-Epoxy-β-silylpropanal with Bases in the Presence of Alkylating AgentsReaction of O-silyl cyanohydrin derivatives of α, β-Epoxy-β-silylpropanal with a strong base such as LDA, NHMDS in the presence of alkyl iodide afforded 2-alkylated derivatives of 2, 4-bis (siloxy)-3-butenenitrile as a single isomer in excellent yields. The fact that no O-alkylated and 4-alkylated products were obtained suggests that the tandem processes involving proton abstraction/epoxide ring opening/Brook rearrangement/allylic rearrangement/alkylation would occur in a concerted manner. The use of readily available optically active epoxides in the reaction seems very promising for construction of quaternary chiral centers and will be the subject of further studies.

这项研究的目的是基于α，β-氧基硅烷与核恐惧症的反应开发新的合成反应。1。当用乙烯基乙烷处理γ-丙烯酰乙酰苯二甲烷时，立体特定的构造是通过乙烯基硫烷治疗的，通过1，2-二甲基甲基甲基二酸酯的重新构造的1、2-二甲基甲基甲基化生成的含氧基氧基重排，以单个氧基氧化的重排作为单个非洲氧化含量重排作为单个非洲蛋白非可含氧化合物。乙烯基。此外，我们发现了一种更通用的方法，用于合成碳循环的方法，涉及γ-乙烯基-γ-甲硅烷基-γ-乳激反应，该反应是由β-甲氧基碳硅烷与乙烯基硫烷与乙烯基硫硫烷一起制备的。在α，β-氧基-β-硅胶丙二甲基丙烷的反应中，在存在α，β-氧基β-甲基甲硅烷基丙二甲粉的O-硅烷基氰氢衍生物的烷基化剂中存在烷基化剂的存在，并具有强大的基础，例如lda的强大基础，nhm nhms的存在，β-环氧基 - β-甲基甲硅烷基丙二醇属性具有强大的基础。 2，4双（siloxy）-3-丁叶作为单个异构体，具有出色的产率。未获得O-烷基化和4-烷基化产物的事实表明，涉及质子抽象/环氧环开放/布鲁克重排/烯丙基重排/烷基化的串联过程将以协同的方式进行。在反应中使用易于使用的光活性环氧化物似乎非常有希望用于建造第四纪手性中心，并且将成为进一步研究的主题。