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酰胺基团导向普通烷烃C—H键的选择性功能化
  • ISSN号:0567-7351
  • 期刊名称:化学学报
  • 时间:2015
  • 页码:1250-1274
  • 期号:12
  • 便笺:31-1320/O6
  • 分类:O623.11[理学—有机化学;理学—化学]
  • 作者地址:上海交通大学化学系;
  • 作者机构:上海交通大学化学系,上海200240
  • 相关基金:国家自然科学基金(No.21372153)资助
中文摘要:

酰胺基团常见于天然产物和药物分子中,利用它们的导向作用完成其普通烷烃C—H键的选择性功能化的相关反应研究在近十年内已取得迅速发展,并且这类反应也将逐渐成为构筑分子骨架、延长碳链和引入官能团的理想方法.本文对过去十年该领域的进展按成键形式、反应物类型分类并以时间顺序排列,依次叙述生成烷烃芳烃、烷烃烯烃、烷烃羰基、烷烃炔烃及烷烃烷烃结构的碳碳键和碳氮、碳氧等碳杂原子键的反应.论述主要集中在反应的表现、改进及其合成应用,以及反应机理讨论等.

英文摘要:

Normal alkyl C—H bonds refer to those sp~3 C—H bonds not linking with any carbon functional groups or heteroatoms at their adjacent positions. They are fundamental chemical bonds, which are widespread both in raw materials such as petroleum oil, natural gas etc. for chemical industries and in various kinds of intermediates for chemical syntheses. Selective transformation of these ubiquitous alkyl C—H bonds into new carbon-carbon, carbon-nitrogen, or carbon-oxygen bonds is an ideal method in construction of molecular skeletons, extension of carbon-chains and introduction of functional groups, which is urgently desired in either large-scale production or laboratory synthesis. However, these normal sp~3 C—H bonds are extremely chemical inert, due to their high bond dissociation energy and low acid dissociation constant. Thus, they are not used directly and conveniently as other available functional groups in synthetic chemistry. Since the beginning of this century, the functionalization of normal alkyl C—H bonds has been developed rapidly through C—H activation which is to cleave these inert C—H bonds with the assistance of some special directing groups by use of catalytic transition-metal complexes under mild conditions. Amides as one of the effective directing groups, which are prevalent in natural products and pharmaceuticals, has also received particular attention. A series of novel reactions using various amides as directing groups to produce carbon-carbon and carbon-heteroatom bonds, including alkyl-aryl, alkyl-alkenyl, alkyl-carbonyl, alkyl-alkynyl, alkyl-alkyl linkages and carbon-nitrogen, carbon-oxygen, carbon-chlorine, carbon-bromine, carbon-boron, carbon-sulfur, carbonselenium bonds, etc. have been established, and some of them have been applied to the practical synthesis already. This review describes the development on the functionalization of normal alkyl C—H bonds according to the formed bonds, reaction substrates, and chronological order. It is emphasized that the structures of amide

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694