基于钯催化的C-H官能化合成平面手性化合物及芳基酮化合物的研究

发布时间：2018-03-22 07:36

本文选题：平面手性　切入点：Catellani反应　出处：《中国科学技术大学》2017年博士论文　论文类型：学位论文

【摘要】：本论文主要分为四个部分:平面手性二茂铁化合物的合成、Catellani反应的研究进展、通过Catellani反应合成二芳基酮衍生物及通过Catellani反应合成芳基烷基酮衍生物,论文内容主要包括如下四章:第一章:钯催化的不对称分子内C-H官能团化合成平面手性化合物平面手性化合物从1966年发现以来就引起了广泛的关注。利用它可以得到具有面手性的配体及催化剂。我们报道了一种Pd(0)催化的高效合成手性二茂铁衍生物的方法。反应通过分子内C-H官能团化,不对称合成具有立体专一性的二茂铁类化合物。该反应具有以下几个特点:1,反应迅速,底物简单;2,反应使用的膦配体为易得的手性BINAP;第二章:Catellani反应的研究进展本章主要简述了 Catellani反应的多种淬灭方式和最近的几年中发展的多种新型亲电试剂以及Catellani反应在全合成中的应用和发展。第三章:Catellani反应合成二芳基酮类化合物的研究二芳基酮类化合物存在于自然界很多天然产物中。本章主要研究了利用Catellani反应合成二芳基酮衍生物。反应以芳基酰氯作为亲电试剂,最后通过Heck反应进行淬灭。成功的实现了 Catellani反应对芳基碘代物的邻位酰基化。通过优化条件发现,反应需要加入当量的水,通过对动力学的研究发现,反应的活性酰基化试剂可能是酸酐。X-ray单晶衍射确定了该化合物的结构。第四章:Catellani反应合成芳基烷基衍生物的研究芳基烷基酮类化合物存在于很多天然产物和药物中间体中。本章主要介绍了利用Catellani反应合成芳基烷基酮类化合物。通过制备混合酸酐作为亲电试剂,研究了 Catellani反应的酰基化作用对于吸电子基团和供电子基团的选择性。
[Abstract]:This thesis is divided into four parts: the synthesis of planar chiral ferrocene compounds Catellani reaction, the synthesis of diaryl ketone derivatives by Catellani reaction and the synthesis of aryl alkyl ketones derivatives by Catellani reaction. The main contents of this paper are as follows: chapter 1: Palladium catalyzed synthesis of planar chiral compounds by asymmetric intramolecular C-H functionalization has attracted wide attention since its discovery in 1966. An efficient method for the synthesis of chiral ferrocene derivatives catalyzed by PD _ 0 was reported. The reaction was carried out by intramolecular C-H functionalization. Asymmetric synthesis of ferrocene compounds with stereospecific properties. The reaction has the following characteristics: 1, the reaction is rapid, A simple substrate with phosphine ligands used in the reaction is a readily available chiral BINAP.Chapter 2: Catellani reaction advances in this chapter this chapter mainly describes the various quenching methods of the Catellani reaction and the recent development of a variety of new electrophilic reagents as well as Catellani. Application and Development of reaction in Total Synthesis. Chapter 3 study on the Synthesis of Diaryl ketones by the reaction of: Catellani; Diarylketones are found in many natural products of nature. In this chapter, the synthesis of diarylketones by Catellani reaction is studied. Derivatives of aryl ketones. Reaction using aryl chloride as an electrophilic reagent, Finally, the Heck reaction was used to quench the aryl iodides successfully. Through the optimization of the conditions, it was found that the reaction needed to add equivalent water, and through the study of kinetics, it was found that, The active acylation reagents of the reaction may be the anhydride. X-ray single crystal diffraction to determine the structure of the compound. Chapter 4 study on the Synthesis of aryl Alkyl Derivatives by the reaction of: Catellani; aryl alkyl ketones are found in many natural products and drugs. In this chapter, the synthesis of aryl alkyl ketones by Catellani reaction is introduced. The selectivity of the acylation of the Catellani reaction to the electron-absorbing and donor groups was studied.
【学位授予单位】：中国科学技术大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251

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