Abstract
A novel reaction of acylium and thioacylium ions, polar [4 + 2^+^] Diels–Alder cycloaddition with 1,3‐dienes and O‐heterodienes, has been systematically investigated in the gas phase (Eberlin MN, Cooks RG. J. Am. Chem. Soc. 1993; 115: 9226). This polar cycloaddition, yet without precedent in solution, likely forms cyclic 2,5‐dihydropyrylium ions. Here we report the reactions of gaseous acylium ions [(CH~3~)~2~N—C^+^O, Ph—C^+^O, (CH~3~)~2~N—C^+^S, CH~3~—C^+^O, CH~3~CH~2~—C^+^O, and CH~2~CH—C^+^O] with several 1‐oxy‐substituted 1,3‐dienes of the general formula RO—CHCH—C(R^1^)CH~2~, which were performed to collect further evidence for cycloaddition. In reactions with 1‐methoxy and 1‐(trimethylsilyloxy)‐1,3‐butadiene, adducts are formed to a great extent, but upon collision activation they mainly undergo structurally unspecific retro‐addition dissociation. In reactions with Danishefsky's diene (trans‐1‐methoxy‐3‐(trimethylsilyloxy)‐1,3‐butadiene), adducts are also formed to great extents, but retro‐addition is no longer their major dissociation; the ions dissociate instead mainly to a common fragment, the methoxyacryl cation of m/z 85. This fragment ion is most likely formed with the intermediacy of the acyclic adduct, which isomerizes prior to dissociation by a trimethylsilyl cation shift. Theoretical calculations predict that meta cycloadducts bearing 1‐methoxy and 1‐trimethylsilyloxy substituents are unstable, undergoing barrierless ring opening induced by the charge‐stabilizing effect of the 1‐oxy substituents. In contrast, for the reactions with 1‐acetoxy‐1,3‐butadiene, both the experimental results and theoretical calculations point to the formation of intrinsically stable cycloadducts, but the intact cycloadducts are either not observed or observed in low abundances. Both the isomeric ortho and meta cycloadducts are likely formed, but the nascent ions dissociate to great extents owing to excess internal energy. The ortho cycloadducts dissociate by ketene loss; the meta cycloadducts undergo intramolecular proton transfer to the acetoxy group followed by dissociation by acetic acid loss to yield aromatic pyrylium ions. Either or both of these dissociations, ketene and/or acetic acid loss, dominate over the otherwise favored retro‐Diels–Alder alternative. The pyrylium ion products therefore constitute compelling evidence for polar [4 + 2^+^] cycloaddition since their formation can only be rationalized with the intermediacy of cyclic adducts. Copyright © 2003 John Wiley & Sons, Ltd.