Unexpected δ-Substitution Products

Significance

The authors report a chiral primary amine 3 catalyzed reaction of cyclic Morita-­Baylis-Hillman (MBH) adducts 1 with indoles 2, in which unexpected δ-substitution products 4 were obtained in high enantioselectivities. This transformation proceeded well in the presence of 20 mol% of primary amine catalyst 3 and 40 mol% TFA as cocatalyst at room temperature, providing various δ-substitution products 4 in high yields (68-92%) and high enantiomeric purity (er up to 96.5:3.5). N-Methylindole was less reactive and enantioselective under the same reaction conditions. The reactions of cyclohexenone-derived MBH alcohols or alkyl- instead of aryl-substituted ones did not give the desired products.