Controllable Fluorocarbon Chain Elongation: TMSCF 2 Br-Enabled Trifluorovinylation and Pentafluorocyclopropylation of Aldehydes

作者：An Liu, Xianghong Zhang, Feng Zhao, Chuanfa Ni, Jinbo Hu · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c12919 · 被引用次数：16 · 研究领域：Fluorine in Organic Chemistry、Cyclopropane Reaction Mechanisms、Synthesis and Reactions of Organic Compounds

Controllable fluorocarbon chain elongation (CFCE) is a promising yet underdeveloped strategy for the well-defined synthesis of structurally novel polyfluorinated compounds. Herein, the direct and efficient trifluorovinylation and pentafluorocyclopropylation of aldehydes are described by using TMSCF 2 Br (TMS = trimethylsilyl) as the sole fluorocarbon source, accomplishing the goals of CFCE from C 1 to C 2 and from C 1 to C 3, respectively. The key to the success of these CFCE processes lies in the unique and diversified chemical reactivity of TMSCF 2 Br, which can serve as two different precursors, namely, a TMSCF 2 radical precursor and a difluorocarbene precursor. Various functional groups are amenable to this new synthetic protocol, providing streamlined access to a broad range of alcohols containing trifluorovinyl or pentafluorocyclopropyl moieties from abundantly available aldehydes. The potential utility of these methods is further demonstrated by the gram-scale synthesis, derivatization, and measurement of log P values of the products.