Ene‐ene‐yne Reactions: Activation Strain Analysis and the Role of Aromaticity

Abstract

The trend in reactivity of the thermal cycloisomerization reactions of 1,3-hexadien-5-ynes, A=B-C=D-E≡F, were explored and analyzed by using density functional theory at the M06-2X/def2-TZVPP level. These reactions proceed through formally aromatic transition states to form a bent-allene intermediate with relatively high activation barriers. Activation-strain analyses show that the major factor controlling this Hopf cyclization is the geometrical strain energy associated with the rotation of the terminal [A] group. This rotation is necessary for achieving a favorable HOMO-LUMO overlap with the yne-moiety [F] associated with the formation of the new A-F single bond. In addition, the relationship between the aromaticity of the corresponding cyclic transition states (all six-membered rings) and the computed activation barriers were analyzed. The calculations also indicate that the aromatization of the bent-allene structures takes place through two consecutive 1,2-hydrogen shifts, the second one exhibiting negligible energy barriers.