物理化学学报 >> 2019, Vol. 35 >> Issue (9): 954-967.doi: 10.3866/PKU.WHXB201810044

所属专题: 碳氢键活化

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C―H官能化构建硫醚

陈世豪1,王明1,姜雪峰1,2,*()   

  1. 1 华东师范大学化学与分子工程学院,上海市绿色化学与化工过程绿色化重点实验室,上海 200062
    2 中国科学院上海有机化学研究所,金属有机化学国家重点实验室,上海 200032
  • 收稿日期:2018-10-22 录用日期:2018-11-26 发布日期:2018-11-29
  • 通讯作者: 姜雪峰 E-mail:xfjiang@chem.ecnu.edu.cn
  • 作者简介:姜雪峰,2003年获西北大学学士学位,2008年于中国科学院上海有机研究所获博士学位。现任华东师范大学教授、博导、教育部“青年长江学者”。研究方向为有机硫化学和方法学导向的天然产物全合成
  • 基金资助:
    国家重点研发计划(2017YFD0200500);国家自然科学基金(21722202);国家自然科学基金(21672069);国家自然科学基金(21472050);国家自然科学基金(21502054);上海市基础研究领域项目(18JC1415600);中组部“万人计划”青年拔尖人才资助

C―H Functionalization Strategies for the Construction of Thioethers

Shihao CHEN1,Ming WANG1,Xuefeng JIANG1,2,*()   

  1. 1 Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering
    2 East China Normal University, Shanghai 200062, P. R. China
  • Received:2018-10-22 Accepted:2018-11-26 Published:2018-11-29
  • Contact: Xuefeng JIANG E-mail:xfjiang@chem.ecnu.edu.cn
  • Supported by:
    the National Key Research and Development Program of China(2017YFD0200500);National Natural Science Foundation of China(21722202);National Natural Science Foundation of China(21672069);National Natural Science Foundation of China(21472050);National Natural Science Foundation of China(21502054);S&TCSM of Shanghai, China(18JC1415600);National Program for Support of Top-notch Young Professionals, China

摘要:

硫醚作为一类重要的含硫功能分子,广泛存在于天然产物、药物及有机发光材料中。鉴于硫醚类化合物的重要性,近年来化学家们发展了一系列高效构建硫醚的方法。与传统的有机卤化物/有机硼酸与硫醇交叉偶联的合成方法相比,C―H官能化直接构建硫醚的策略因其步骤经济性、原子经济性备受合成化学家们关注,并取得重要进展。本文根据不同过渡金属进行分类,系统阐述了近年来过渡金属催化/参与C―H官能化或无过渡金属催化C―H官能化构建硫醚这一方向研究进展。

关键词: 硫醚, C―H官能化, 过渡金属, 无过渡金属催化, 含硫化合物

Abstract:

Thioesters, which are essential sulfur-containing organic molecules, are indispensable in natural products, pharmaceuticals, and organic light-emitting materials. Efficient synthesis of thioethers has received considerable attention due to the widespread applications of these compounds, and many fundamental approaches for C―S bond formation have been proposed. However, most of them construct C―S bonds by employing organic halides/organic boronic acid. These methodologies generally suffer from a pre-functionalized starting material. Recently, selective C―H functionalization emerged as a powerful tool for the synthesis of C―N, C―O, C―C, and C-halogen bonds. Nevertheless, C―S bond formation via C―H functionalization has only recently been given more importance because organosulfur compounds are believed to inactivate catalysts. In contrast to traditional cross-coupling reactions, direct functionalization of C―H bonds for the synthesis of thioethers can shorten the reaction steps and minimize the amount of waste formed. In this review, which is divided into several parts, we describe C―H functionalization strategies for the construction of thioethers. In Part Ⅰ, we introduce the importance and widespread applications of thioethers in daily life. For example, Lissoclibadin 6 is a polysulfur aromatic alkaloid that shows antimicrobial activity. Seroquel is an antipsychotic medicine. It is used to treat bipolar disorder and schizophrenia in adults, and children who are at least 10 years old. Tazarotene is approved for the treatment of psoriasis, acne, and sun-damaged skin. Furthermore, a comparison between conventional synthesis methods and C―H thiolation is discussed. In Part Ⅱ, we introduce copper-catalyzed or copper-mediated C―H thiolation. Along with the direct functionalization of sp2 and sp C―H for the synthesis of aryl sulfides, some significant and challenging thiolations of sp3 C―H are included. In addition to copper, palladium is an excellent catalyst for C―H functionalization. In Part Ⅲ, we elucidate palladium-catalyzed C―H thiolation and discuss many proposed mechanisms. Nickel, which is a first-flow, low-cost, and earth-abundant metal catalyst, has increasingly gained attention. In contrast to copper and palladium, despite its late start, several remarkable reports on nickel-catalyzed C―H thiolation were published by several groups. Rhodium plays a key role in selective C―H functionalization. Some published results proved the capacity of rhodium catalysts to promote C―S construction via C―H functionalization. In Part Ⅳ, we introduce rhodium-catalyzed C―H thiolation. In recent years, metal-free C―H functionalization has been quite attractive. In Part Ⅴ, some C―S construction strategies via metal-free C―H functionalization are presented. In the last part, the conclusion discusses the limitations and possible development directions of these advances in the construction of thioethers.

Key words: Thioethers, C―H functionalization, Transition metal, Transition metal-free catalysis, Sulfur-containing compounds

MSC2000: 

  • O643