Radical Cyclization of Fluorinated 1,3‐Dicarbonyl Compounds with Dienes Using Manganese(III) Acetate and Synthesis of Fluoroacylated 4,5‐Dihydrofurans

Abstract

AbstractRadical cyclizations of fluorinated 1,3‐dicarbonyl compounds with dienes mediated by Mn(OAc)3 afforded 4,5‐dihydrofurans containing difluoroacetyl, trifluoroacetyl, or heptafluorobutanoyl groups in good‐to‐excellent yields. Additionally, 2‐(difluoromethyl)‐4,5‐dihydrofurans and a 4,7‐dihydrooxepin derivative were obtained as unexpected products in the reaction of 4,4‐difluoro‐1‐phenylbutane‐1,3‐dione with 1,3‐diphenylbuta‐1,3‐diene. The radical cyclization of symmetrical dienes such as 2,3‐dimethylbuta‐1,3‐diene and 1,4‐diphenylbuta‐1,3‐diene with 1,3‐diketones furnished the corresponding products in low yields. However, treatment of 1‐phenylbuta‐1,3‐diene with 1,3‐dicarbonyl compounds afforded 4,5‐dihydrofurans containing fluoroacyl groups. The radical cyclizations with 3‐methyl‐1‐phenylbuta‐1,3‐diene and 1,3‐diphenylbuta‐1,3‐diene led to 4,5‐dihydrofurans in good yields, since Me and Ph groups at C(3) of these dienes increase the stability of the radical intermediate.