Synthesis of [5.5.5.5]fenestranes by pd-catalyzed carbonylation-cyclisation

Novel Oxidative Rearrangement Product of the Firsttrans,cis,cis,cis-[5.5.5.5]Fenestrane Derivative

“…This connectivity feature gives rise to unique topologies along with the potential for severe strain. Several syntheses of the cis,cis,cis,cis- [5.5.5.5]fenestranes have been reported (Thommen, Gerber & Keese, 1991;Keese, Guidetti-Grept & Herzog, 1992). Prior to the current work, however, no synthesis of a trans, cis,cis,cis-[5.5.5.5]fenestrane system had been reported, despite impressive efforts toward this goal (Luyten & Keese, 1986).…”

Transition Metal-Catalyzed Carbocyclizations in Organic Synthesis

“…71 The "palladium-ene" reaction of 1,6-diene 52 followed by carbonylative cyclization, i.e., carbonylative double annulation, gives the corresponding [5.5.5.5]fenestranes 53a and 53b (eq 61). 130 This process is applicable to 1,6-diynes as well.…”

A [5.5.5.5]Fenestrane Derivative

“…Recently, several methods involving transition metals have been used to synthesize novel fenestranes (Thommen, Gerber & Keese, 1991;van der Waals & Keese, 1992;Keese, Guidetti-Grept & Herzog, 1992). One method, the palladium-catalyzed carbonylationcyclization of the bicycle (1), yields the ketoacid (2) which, in CDC13 solution, exists in equilibrium with the pseudoacid (3) (Keese, Guidetti-Grept & Herzog, 1992).…”