羰基兼容的氟代反应及远端氟代脂肪酮合成的近期进展  

Recent Advances in the Synthesis of Distal Fluorinated Ketones

作　　者：范雪峰[1] 赵会君[1] 朱晨[1] 

机构地区：[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

出　　处：《化学学报》2015年第10期979-983,共5页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21402134)资助~~

摘　　要：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.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 a-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 sp^3 C--H fluorination, decarboxylative fluorination, and deboronofluorination to construct aliphatic sp^3 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 sp^3 C--H fluorination and the synthesis of distal fluorinated ketones.

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 

分 类 号：O621.3[理学—有机化学]