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化学进展 2016, Vol. 28 Issue (1): 1-8 DOI: 10.7536/PC150906 前一篇   后一篇

• 综述与评论 •

环丁醇开环官能化反应:通过C—C键断裂区域选择性构建γ位取代脂肪酮的新策略

晏宏, 朱晨*   

  1. 苏州大学材料与化学化工学部 江苏省有机合成重点实验室 苏州 215123
  • 收稿日期:2015-09-01 修回日期:2015-10-01 出版日期:2016-01-15 发布日期:2015-12-21
  • 通讯作者: 朱晨 E-mail:chzhu@suda.edu.cn
  • 基金资助:
    国家自然科学基金项目(No.21402134)和江苏省自然科学基金项目(No.BK20140306)资助
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Ring Openings of tert-Cyclobutanols: New Strategy towards the Synthesis of γ-Substituted Ketones via C—C Bond Cleavage

Yan Hong, Zhu Chen*   

  1. Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
  • Received:2015-09-01 Revised:2015-10-01 Online:2016-01-15 Published:2015-12-21
  • Supported by:
    The work was supported by the National Natural Science Foundation of China (No. 21402134) and the Jiangsu Provincial Natural Science Foundation of China(No. BK20140306).
环丁醇开环官能化反应是制备γ位取代脂肪酮的重要策略之一。通过区域选择性的C—C键断裂和新化学键(例如:C—C、C—N、C—O、C—F键等)的构建,环丁醇开环反应可以高效地在羰基的γ位引入各种各样的取代基团。环丁醇的开环反应途径主要分为两种:1)通过过渡金属钯和铑催化的β-碳消除反应开环;2)自由基历程的环丁醇单电子氧化开环。本文依据不同的开环反应机理,对环丁醇的开环官能化反应进行了阐述和展望。
关键词： 环丁醇, γ位取代脂肪酮, 开环反应, C—C键断裂, β-碳消除反应, 自由基
Ketone is an important structural moiety in organic chemistry due to its wide occurrence in organic compounds and the highly transformable ability into other functionalities. Therefore, the efficient synthesis of ketones is of great significance. Recently, the ring-opening functionalization of tert-cyclobutanols represents one of the most important approaches to synthesize γ-substituted alkyl ketones. A variety of functional groups can be efficiently introduced to the γ-position of carbonyl via the regioselective C—C bond cleavage and a new chemical bond (C—C, C—N, C—O, C—F, etc.) formation. Two major pathways might be involved in the ring-opening reactions of tert-cyclobutanols: a) transition metals, such as Pd(Ⅱ) and Rh(Ⅰ), catalyzed β-carbon elimination of tert-cyclobutanols, and b) radical-mediated ring opening via the single electron oxidation of tert-cyclobutanols. The recent advances in the ring openings of tert-cyclobutanols and the related mechanistic details are described in this review.

Contents
1 Introduction
2 Transition-metal catalyzed ring openings of tert-cyclobutanols via β-carbon elimination
2.1 Pd-catalyzed ring-opening reactions of tert-cyclobutanols
2.2 Rh-catalyzed ring-opening reactions of tert-cyclobutanols
3 Radical-mediated ring openings of tert-cyclobutanols
3.1 Oxidative ring opening of tert-cyclobutanols to construct carbon-carbon bond
3.2 Oxidative ring opening of tert-cyclobutanols to construct carbon-heteroatom bonds
4 PIDA-mediated ring-opening hydroxylation of tert-cyclobutanols via carbocation pathway
5 Conclusion and outlook

Key words: tert-cyclobutanol, γ-substituted ketone, ring opening, C—C bond cleavage, β-carbon elimination, radical

中图分类号: 

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