title: 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.
authors.affiliation: Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid (Spain). israel@quim.ucm.es.
authors.forename: Israel
authors.initials: I
authors.lastname: Fernández
authors.forename: F Matthias
authors.initials: FM
authors.lastname: Bickelhaupt
authors.forename: Fernando P
authors.initials: FP
authors.lastname: Cossío
keywords: aromaticity; cyclization; density functional calculations; reactivity; transition states