化学学报 ›› 2015, Vol. 73 ›› Issue (10): 979-983.DOI: 10.6023/A15060424 上一篇    下一篇

研究亮点

羰基兼容的氟代反应及远端氟代脂肪酮合成的近期进展 2016 Awarded

范雪峰, 赵会君, 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:2015-06-19 出版日期:2015-10-15 发布日期:2015-09-15
  • 通讯作者: 朱晨 E-mail:chzhu@suda.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No.21402134)资助.

Recent Advances in the Synthesis of Distal Fluorinated Ketones

Fan Xuefeng, Zhao Huijun, Zhu Chen   

  1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123
  • Received:2015-06-19 Online:2015-10-15 Published:2015-09-15
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21402134).

含氟化合物在医药、农药以及材料领域有着广泛的应用, 然而温和而高效的构建sp3碳氟键却极具挑战性. 氟代脂肪酮类化合物是一类重要的含氟合成砌块. 本文将从碳氢键氟化、脱羧脱硼氟化、双键氟化、开环氟化四个方面简要概述近年来羰基兼容的氟代反应以及在合成远端氟代脂肪酮方面取得的重要进展.

关键词: 氟化反应, 碳氢键活化, 脱羧反应, 烯烃双官能团化, 开环反应

Incorporation of a fluorine atom to molecules is a privileged strategy to modify the physical, chemical and biological properties, which is widely executed in pharmaceuticals, agrochemical and material sciences. Consequently, the development of efficient and direct fluorination approach is of considerable significance. In spite of the great progress made in the transition-metal catalyzed construction of sp2 C—F bond via C—H activation and cross-coupling reactions, the direct access to aliphatic sp3 C—F bond is relatively underdeveloped as the development of a mild and efficient method to construct sp3 C—F bond remains a challenging issue. Ketone is a ubiquitous and important structural motif in organic compounds. The efficient synthesis of fluorinated ketone building blocks thus provides a shortcut for the introduction of fluorinated functionalities into complex molecules. Other than α-fluorinated ketones, the synthesis of distal fluorinated ketones is still challenging. Herein, we highlight the recent efforts made for the synthesis of distal fluorinated ketones. Four fluorination pathways are described: (a) C—H fluorination, (b) decarboxylative fluorination and deboronofluorination; (c) olefin fluorination, and (d) ring-opening fluorination. The first and second sections briefly introduce the direct sp3 C—H fluorination, decarboxylative fluorination, and deboronofluorination to construct aliphatic sp3 C—F bonds, which are tolerant to carbonyl group in the substrates. The third section discusses the direct construction of β and γ-fluorinated ketones via the difunctionalization of olefins. The last section puts an emphasis on the latest emergence of ring-opening fluorination. Relying on the “radical clock” strategy, the distal fluorinated ketones can be obtained from the corresponding tertiary cycloalkanols. Overall, this highlight provides a new insight into the recent advances in the sp3 C—H fluorination and the synthesis of distal fluorinated ketones.

Key words: fluorination, C—H activation, decarboxylation, olefin difunctionalization, ring opening