Stereoselective Intramolecular [2+2] Trapping of 1,2-Cyclohexadienes: a Route to Rigid, Angularly Fused Tricyclic Scaffolds.

1,2-Cyclohexadienes generated under mild fluoride-mediated desilylative conditions undergo efficient intramolecular [2+2] trapping, providing tricyclic alkylidene cyclobutanes with complete diastereoselectivity for the cis-fused products. Pendent styrenes or electron-deficient olefins can trap simple 1,2-cyclohexadienes or their oxygenated counterparts, with 14 substrates being disclosed. Reactions proceed at ambient temperature using just cesium fluoride in up to 91 % yield, and the necessary precursors are easily accessed from substituted 2-bromocyclohexenones. Multiple synthetic routes have been developed to install the appropriate functional groups required for [2+2] trapping.

Strain-Activated Diels-Alder Trapping of 1,2-Cyclohexadienes: Intramolecular Capture by Pendent Furans.

Intramolecular [4 + 2] cycloaddition reactions of substituted 1,2-cyclohexadienes with pendent furans enables the synthesis of complex tetracyclic scaffolds in a single step under mild conditions. All Diels-Alder cycloadducts were obtained as single diastereomers, assigned as the endo isomer. Substrates were easily assembled via Stork-Danheiser alkylation of 3-ethoxy-2-bromocyclohex-2-enone to accommodate a range of tethers and furan traps. Cleavage of enol acetate moieties resulted in room-temperature Diels-Alder cycloreversion to tethered furyl cyclohexenones.

Formation and Trapping of Azafulvene Intermediates Derived from Manganese-Mediated Oxidative Malonate Coupling.

The one-pot, three-component, coupling reaction of indoles/pyrroles, dimethyl malonate, and acetic acid was performed using Mn(III) acetate as an oxidant. In the presence of Mn(OAc)3, indole-2, and indole-3-carbonyl compounds were alkylated at the 3- and 2- positions, respectively, with subsequent oxidation and nucleophilic capture occurring at the newly formed benzylic carbon. In contrast, oxidation of 2- and 3-indole carboxylic acids afforded the corresponding 2-oxindol-3-ylidenes and 3-oxindol-2-ylidenes. The reaction conditions, scope, and mechanism are discussed herein.

Efficient Trapping of 1,2-Cyclohexadienes with 1,3-Dipoles.

1,2-Cyclohexadienes are transient intermediates that undergo rapid dimerization and intermolecular trapping with activated olefins and heteroatomic nucleophiles. Fluoride-mediated desilylative elimination of readily accessible 6-silylcyclohexene-1-triflates allows the mild, chemoselective, and functional-group tolerant generation of cyclic allene intermediates, which undergo efficient trapping reactions with stable 1,3-dipoles. The reactions proceed with high levels of both regio- and diastereoselectivity. The reaction of cyclic allenes with azides is accompanied by the facile loss of dinitrogen, resulting in the formation of tetrahydroindoles or polycylic aziridines depending on the azide employed.