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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Enantioselective Construction of Fluorinated Tertiary Stereocenters by Rh-Catalyzed [2 + 2 + 2] Cycloaddition of
Shintaro Hamada1, Yu Sato1, Yoshinobu Komiya1
1Department of Chemical Science and Engineering, Institute of Science Tokyo, O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
Abstract:
We report the enantioselective construction of fluorinated tertiary stereocenters via [2 + 2 + 2] cycloaddition between 1,6-enynes and α-fluoroacrylamides using a chiral cationic Rh(I) catalyst at room temperature with full retention of the fluorine atom. Coordination of the amide carbonyl to Rh may promote insertion and suppress β-fluoride elimination, enabling efficient formation of fluorinated cyclic products with high enantioselectivity. This strategy provides streamlined access to complex bicyclic systems bearing fluorinated tertiary stereocenters from readily available starting materials.
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