Structurally original oxathioethers macrocycles containing an exocyclic double-bond: synthesis, characterization, reactivity, and coordination

摘要

New oxathioethers macrocycles have been synthesized and characterized. Each macrocycle consists in structurally defined ether and thioether moieties and an exocyclic double-bond (2a-c) or a hydroxymethyl group (3a-c). Macrocycles (2a-c) have been synthesized by reaction of dianions of thioethers diols (1a-c) with 3-chloro-2-chloromethylprop-1-ene. Their hydroboration/oxidation led to corresponding primary alcohols (3a-c). Structures of compounds (2b) and (3a) have been determined by Xray diffraction. The reactivity of the hydroxyl group allowed the preparation of oxathioethers macrocycles bearing a polyether chain or a benzyl group (4a,b) and the synthesis of new bicyclic sandwich-type compounds (5a,b). The ability of these functionalized macrocycles to coordinate to palladium has been investigated.