(2,5)-Ene cyclization catalyzed by mesoporous solid acids: isotope labeling study and ab initio calculation for continuum from concerted to stepwise ene mechanism.
(2,5)-Ene reactions catalyzed by mesoporous solid acids are reported from the mechanistic point of view. The continuum (2,5)-ene mechanism from the concerted to the cationic cyclization followed by 1,2-hydride shift is evaluated. The solid-acid-catalyzed cyclization of the oxonium ion intermediate 4 derived from cyclic allylic lactol ether 3 bearing allylic hydroxy group affords the (2,5)-ene product as the enol form, eventually tautomerizing to the corresponding aldehyde 6. The continuum from the concerted to stepwise mechanism is experimentally and theoretically verified in the present ene cyclization of the oxonium ion intermediate such as 4. The stepwise cyclization leading to aldehyde 6 is thus shown to associate with the concerted version as a result of the stabilization of the beta-hydroxycarbenium ion intermediate.
Mikami
Koichi
K
Department of Applied Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552 Japan. kmikami@o.cc.titech.ac.jp
Ohmura
Hirofumi
H
Yamanaka
Masahiro
M