Chiral 1,1‘-Binaphthyl-2,2‘-diammonium Salt Catalysts for the Enantioselective Diels−Alder Reaction with α-Acyloxyacroleins

• DOI: 10.1021/ol060490l
• Publication Date: 2006-05-18T05:08:26Z
• Authors: Akira Sakakura; Kenji Suzuki; Kazuhiko Nakano; Kazuaki Ishihara
• Keywords: 01 natural sciences; 0104 chemical sciences

[reaction: see text] A diammonium salt of chiral 1,1'-binaphthyl-2,2'-diamine and trifluoromethanesulfonimide (Tf(2)NH) shows excellent catalytic activity and enantioselectivity for the Diels-Alder reaction of alpha-acyloxyacroleins with cyclic dienes. For example, in the presence of 5 mol % of the ammonium catalyst, the Diels-Alder reaction of alpha-(cyclohexanecarbonyloxy)acrolein with cyclopentadiene proceeded in EtCN at -75 degrees C to give the adducts in 88% yield with 92% exo and 91% ee. This catalyst can be easily prepared in situ by mixing the commercially available chiral diamine and Tf(2)NH.