Tandem processes promoted by a hydrogen shift in 6-arylfulvenes bearing acetalic units at ortho position: a combined experimental and computational study

• Main Authors: Mateo Alajarin, Marta Marin-Luna, Pilar Sanchez-Andrada, Angel Vidal
• Format: Article
• Language: English
• Published: Beilstein-Institut 2016-02-01
• Series: Beilstein Journal of Organic Chemistry
• Subjects: acetal; benzindenes; DFT calculations; fulvene; hydrogen shift
• Online Access: https://doi.org/10.3762/bjoc.12.28

6-Phenylfulvenes bearing (1,3-dioxolan or dioxan)-2-yl substituents at ortho position convert into mixtures of 4- and 9-(hydroxy)alkoxy-substituted benz[f]indenes as result of cascade processes initiated by a thermally activated hydrogen shift. Structurally related fulvenes with non-cyclic acetalic units afforded mixtures of 4- and 9-alkoxybenz[f]indenes under similar thermal conditions. Mechanistic paths promoted by an initial [1,4]-, [1,5]-, [1,7]- or [1,9]-H shift are conceivable for explaining these conversions. Deuterium labelling experiments exclude the [1,4]-hydride shift as the first step. A computational study scrutinized the reaction channels of these tandem conversions starting by [1,5]-, [1,7]- and [1,9]-H shifts, revealing that this first step is the rate-determining one and that the [1,9]-H shift is the one with the lowest energy barrier.