Superacid-Catalyzed Reductive Friedel-Crafts Reaction of Arenes Using Arenecarbaldehyde Acetals.
Reaction of 2-aryl-1,3-dioxane with arenes in the presence of a catalytic amount of trifluoromethanesulfonic acid gave the corresponding diarylmethanes in good to excellent yields. The acid-catalyzed Friedel-Crafts benzylation of arenes could altenatively be carried out using arenecarbaldehyde and 1,3-propanediol. The reaction was assumed to proceed through a redox process involving hydride shift from the cyclic acetal moiety to the benzylic carbon. The hydride shift was confirmed by the reaction with 5-ethyl-2-phenyl-4,4,6,6-tetradeuterio-1,3-dioxane, wherein more than 90% deuterium was incorporated into the benzylic carbon of the diphenylmethane. Diphenylmethyl ether Ph(2)CHOCH(2)CH(2)CH(2)OH also reacted with benzene to afford diphenylmethane under the same reaction conditions, suggesting that the ether should be the plausible intermediate that underwent the hydride shift.
Fukuzawa Si
Shin-ichi
Department of Applied Chemistry, Chuo University, Kasuga, Bunkyo-ku, Tokyo 112, Japan, and Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuda, Midori-ku, Yokohama 226, Japan.
Tsuchimoto
Teruhisa
T
Hiyama
Tamejiro
T