A Versatile Access to 1-Cyclopropyl-2-aryl-1,3,5-hexatrienes - Domino Heck-Diels-Alder Reactions of 1,3-Dicyclopropyl-1,2-propadiene

Knoke, Mario; Meijere, Armin de

doi:10.1055/s-2003-36797

Synlett

2003

DOI: 10.1055/s-2003-36797

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A Versatile Access to 1-Cyclopropyl-2-aryl-1,3,5-hexatrienes - Domino Heck-Diels-Alder Reactions of 1,3-Dicyclopropyl-1,2-propadiene

Mario Knoke¹,

Armin de Meijere²

Abstract: An efficient three-step synthesis of 1,3-dicyclopropyl-1,2-propadiene (4) (overall yield 68%) starting from dicyclopropylacetylene was developed. The allene, when coupled with several aryl iodides and aryl bromides under palladium catalysis in the presence of a reactive dienophile, was found to undergo a domino Heck-Diels-Alder reaction to yield 3-(1′-arylalkenyl)-substituted cyclohexenes 9 in moderate to good yields (36-86%).

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Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans

et al. 2021

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Herein, we report a versatile approach for the endocyclic ring opening of bicyclic vinylcyclopropanes triggered by Heck arylations. The key step for this transformation is a β-C-elimination allowing the ring expansion of cyclopropanated pyrroles, piperidines, furans, as well as cyclopentadienes to grant access to the corresponding 1,2-dihydropyridines, 2H-pyrans, 2,3-dihydro-1H-azepines, and 1,4-cyclohexadienes, respectively. Additionally, gem-disubstituted cyclopropanated furans showed unexpected behavior by giving diastereoselectively asymmetrically substituted dienes. Mechanistic studies and theoretical calculations point toward a facile β-C-elimination with a concomitant shift of Pd along the cyclopropane moiety, which can successfully compete with the usual termination step of a Heck reaction via a syn-β-hydride elimination.

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Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans

et al. 2021

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The Heck Reaction Applied to 1,3- and 1,2-Unsaturated Derivatives, a Way towards Molecular Complexity

et al. 2010

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This review is an overview of the last ten years’ use of the Mizoroki–Heck coupling applied to 1,2- and 1,3-dienes. Since both these systems form π-allyl palladium intermediates in Pd(0) coupling, they show particular chemical behavior. Many examples of 1,2-dienes Heck reactions are presented. 1,2-Dienes are important substrates because of their high reactivity that makes them useful building blocks for the synthesis of biologically relevant structures.

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A Versatile Access to 1-Cyclopropyl-2-aryl-1,3,5-hexatrienes - Domino Heck-Diels-Alder Reactions of 1,3-Dicyclopropyl-1,2-propadiene

Cited by 2 publications

References 2 publications

Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans

Heck-Type Coupling of Fused Bicyclic Vinylcyclopropanes: Synthesis of 1,2-Dihydropyridines, 2,3-Dihydro-1H-azepines, 1,4-Cyclohexadienes, and 2H-Pyrans

The Heck Reaction Applied to 1,3- and 1,2-Unsaturated Derivatives, a Way towards Molecular Complexity

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