Straightforward Access to [6]Metacyclophene-based Enynes by an Inter-Intramolecular Tandem Etherification through a One-Pot Double S_NAr Reaction

Abstract

The first application in the enediyne area of an inter-intramolecular tandem one-pot double S N Ar reaction is demonstrated towards the synthesis of new bi-and tricyclic enediynes 1 and 17, respectively. These polyunsaturated macrocycles are very stable and are not prone to rearrange to a diradical species via a Bergman cycloaromatization. The 1,3-substitution pattern on the aromatic ring could impede this thermal process from occurring.

Initiator-free synthesis of interpenetrating polymer networks via Bergman Cyclization

“…In parallel, the precursor enediyne (EDY) of the interpenetrating network was prepared, representing the basis for the second network. (Z)-oct-4-ene-2,6-diyne-1,8-diol (diol-EDY), 48 up to now only scarcely used for the BC process, [49][50][51][52][53][54] was selected, deemed useful due to its stability at ambient conditions, combined with its ease of preparation and the triggerable activation of the BC. For synthesis, the trimethylsilyl (TMS) group was added as a protective moiety on propargyl alcohol, followed by a classical Sonogashira coupling reaction with (Z)-1,2-dichloroethene and subsequent acid-catalyzed deprotection, in turn affording the diol EDY (Figure S1 in supporting information).…”