[7.7]Paracyclophanes from blue-green algae

Journal of the American Chemical Society
1990.0

Abstract

[m.n] Paracyclophanesl were first described by Cram and Steinberg in 195 1 .2 These carbocyclic compounds, known to date only through synthesis, have provided interesting vehicles for host-guest chemistry. We report here the isolation and identification of [7.7]paracyclophanes from two species of cytotoxic blue-green algae belonging to the Nostocaceae. This marks the first time that this class of macrocyclic compounds has been found in Nature. The lack of thermal stability associated with Gilman reagents ( R2CuLi) composed of allylic ligands, recently demonstrated in these laboratories,2 can be used to rationalize the scarcity of successful organocopper reactions involving allylic cuprates in the past decade.3 Indeed, even the preparation of dimeric (allyl),CuLi at -78 "C affords significant percentages of Wurtz-like coupling material ( IS-hexadiene) together with aggregate (allyl)3Cu2Li,2 which as a class of reagents is known to have considerably different chemical reactivities! To circumvent these problems of reagent preparation and thermal instability, we now report a novel route to higher order (HO) allylic cyanocuprates based on direct transmetalations of precursor allylstannanes. The species so formed by this process (Le., R2Cu(CN)Li2, R = an allylic group) are stable at 0 'C yet are extremely reactive toward substitution reactions (vide infra).

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