Thermal Cyclization of Phenylallenes That Contain ortho-1,3-Dioxolan-2-yl Groups: New Cascade Reactions Initiated by 1,5-Hydride Shifts of Acetalic H Atoms

• Published in: Chemistry : a European journal 2013-11, Vol.19 (47), p.16093-16103
• Main Authors: Alajarin, Mateo, Bonillo, Baltasar, Marin-Luna, Marta, Sanchez-Andrada, Pilar, Vidal, Angel
• Format: Article
• Language: English
• Subjects: allenes; cyclization; density functional calculations; naphthalenes; substituent effects
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201301608

A series of 2‐(1,3‐dioxolan‐2‐yl)phenylallenes that contained a range of substituents (alkyl, aryl, phosphinyl, alkoxycarbonyl, sulfonyl) at the cumulenic C3 position were prepared by using a diverse range of synthetic strategies and converted into their respective 1‐(2‐hydroxy)‐ethoxy‐2‐substituted naphthalenes by smooth thermal activation in toluene solution. Electron‐withdrawing groups at the C3 position accelerated these tandem processes, which consisted of 1) an initial hydride‐like [1,5]‐H shift of the acetalic H atom onto the central cumulene carbon atom; 2) a subsequent 6π‐electrocyclic ring‐closure of the resulting reactive ortho‐xylylenes; and 3) a final aromatization step with concomitant ring‐opening of the 1,3‐dioxolane fragment. If the 1,3‐dioxolane ring of the starting allenes was replaced by a dimethoxymethyl group, the reactions led to mixtures of two disubstituted naphthalenes, which were formed by the migration of either the acetalic H atom or the methoxy group, with the latter migration occurring to a lesser extent. Two of the final 1,2‐disubstituted naphthalenes were converted into their corresponding naphtho‐fused dioxaphosphepine or dioxepinone through an intramolecular transesterification reaction. A DFT computational study accounted for the beneficial influence of the 1,3‐dioxolane fragment on the carbon atom from which the H‐shift took place and also of the electron‐withdrawing substituents on the allene terminus. Remarkably, in the processes that contained a sulfonyl substituent, the conrotatory 6π‐electrocyclization step was of lower activation energy than the alternative disrotatory mode. Keeping the heat on: Heating solutions of 2‐(1,3‐dioxolan‐2‐yl)phenylallenes at reflux in toluene caused their conversion into 1‐(2‐hydroxy)ethoxynaphthalenes through cascade processes that were initiated by a hydride‐like [1,5]‐H shift (see scheme, ERC=electrocyclic ring‐closure). DFT calculations disclosed an interesting balance between the two rotatory modes of the 6π‐electrocyclization step, depending on the substituents at the two linking carbon atoms.