摘    要 硅手性中心的光学活性硅烷在自然界中并不存在，它可作为手性试剂、拆分试剂或手性探针等在不对称合成领域具有潜在应用价值,但它的高效合成仍是一个极具挑战性的课题。在过去的几十年中,通过合成化学家的努力,人们已发展了包括手性拆分、手性诱导、不对称催化在内的多种合成方法，但用酶催化立体选择性合成硅中心手性硅烷的研究仍很少。90303

本论文的利用酶催化硅中心二醇失远程对称策略合成了一系列光学活性硅中心手性硅烷。我们制备合成了一系列潜手性含硅二醇，通过脂肪酶催化它与酸酐的单酯化反应以获取硅中心手性硅烷。本研究工作对?种潜手性含硅二醇与?种脂肪酶进行了筛选，系统考察了反应底物，包括含硅二醇中醇羟基的取代位、硅上取代基的电子/空间位阻效应、酸酐的化学结构，以及脂肪酶的类型对反应手性选择性的影响。研究表明脂肪酶（Lipozyme TL IM）能以较高的立体选择性实现对??的远程失对称反应，ee%为?

毕业论文关键词：手性硅烷； 酶催化；失对称；手性选择性

Abstract The optically active silane in the chiral center of silicon does not exist in nature。 It can be used as a chiral reagent, a resolving agent or a chiral probe in the field of asymmetric synthesis, but its efficient synthesis is still a pole Challenging issues。 In the past few decades, through the efforts of synthetic chemists, people have developed a variety of synthetic methods, including chiral resolution, chiral induction, asymmetric catalysis, but with enzyme-catalyzed stereoselective synthesis of silicon center There is still little research on chiral silanes。

In this paper, a series of optically active silicon center chiral silanes were synthesized by using the enzymatic catalytic silicon diol loss-free symmetry strategy。 We prepared a series of latent silicon diols synthesized by lipase catalyzing the monoesterification reaction with the acid anhydride to obtain the silicon center chiral silane。 In this study, the latent silicon diol and the lipase were screened, and the reaction substrate, including the substitution position of the alcoholic hydroxyl group in the silicon-containing diol, the electron / space position of the substituent on the silicon The chemical structure of the acid anhydride, and the type of lipase on the chiral selectivity of the reaction。 Studies have shown that lipase (Lipozyme TL IM) can achieve a high degree of stereoselectivity to achieve a remote disregard response, ee%

Keyword: Chiral silane; enzyme catalysis; desymmetrization;stereoselectivity, organosilicon compound

目    录

摘    要 I

Abstract II

目    录 III

一、引言 1

二、 手性硅烷的合成源Q于W优E尔A论S文R网wwW.yOueRw.com 原文+QQ75201,8766 与应用 1

2。1手性硅烷的合成 1

2。1。1手性诱导构建手性硅烷 1

2。1。2酶催化失对称合成 1

2。1。3过渡金属催化合成 2

2。2手性硅烷的应用 2

2。2。1手性探针研究反应机理 2

2。2。2手性硅烷Brook和Retro-Brook重排 3

三、实验部分 3

3。1实验仪器与试剂 3

3。2实验方法