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Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols
Author(s) -
Okamoto Koichi,
Hori Mitsuki,
Yanagi Tomoyuki,
Murakami Kei,
Nogi Keisuke,
Yorimitsu Hideki
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201809035
Subject(s) - ketene , sigmatropic reaction , chemistry , benzofuran , aromatization , reactivity (psychology) , organic chemistry , combinatorial chemistry , catalysis , medicine , alternative medicine , pathology
Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatropic rearrangement, (2) Zn‐mediated smooth reductive removal of fluoride from the dearomatized intermediate, and (3) acid‐promoted cyclization/aromatization. Mechanistic investigations revealed important characteristic reactivity of polyfluorophenols in the present system. Some of the fluorinated benzofuran products were transformed by utilizing the 2‐methylsulfanyl moieties.