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Ferrocenes were studied as cyclopentadiene ring surrogates enroute to non-metallocene targets such as the aminofulveno[1,2-b]chromone natural product chalaniline A. Ferroceno[b]chromone, as an archetype of interest, was prepared from ferrocenecarboxylic acid (4 steps, 24% yield) via N,N-diethyl 2-iodoferrocenecarboxamide by Ullmann etherification with phenol followed by LDA-mediated anionic cyclization. Reactivity studies revealed that this planar chiral analogue of xanthone readily fragments into non-metallocene products upon reaction with electrophiles. 1-Methoxy-3-methylferroceno[b]chromone, prepared similarly by substituting O-methylorcinol for phenol, was advanced to chalaniline A and a transposed regioisomer by concomitant deferration and demethylation with AlCl3; formylation of the resulting cyclopentadiene-fused chromone with excess Vilsmeier reagent; and then Pinnick oxidation (NaClO2), methylation (TMSCHN2), and final transamination (PhNH2). Four compounds, including ferroceno[b]chromone and the C11/C12-transposed regioisomer of chalaniline A, were characterized by single crystal X-ray diffraction analysis. 

Chalaniline A, an aminofulveno[1,2-b]chromone derivative previously isolated from a vorinostat-treated ascomycete Chalara sp., was prepared in nine steps from orcinol (3,5- dihydroxytoluene). In a key transformation, the tricyclic ring system of the target was generated by a pyrrolidine-catalyzed double annulation between α-(methylsulfinyl)-2,6-dihydroxy-4-methylacetophenone and the ketaldoester, methyl 2,5-dioxopentanoate. The resulting tertiary alcohol (coniochaetone H) was further converted to chalaniline A by operations including dehydration (to yield a hydroxyfulvene), Vilsmeier reaction, and enamine exchange. 

New routes to the formation of macrocyclic molecules are of high interest to the supramolecular chemistry community and the chemistry community at large. Here we describe the incorporation of heterocyclic core units into discrete macrocycles via the utilization of a pnictogen-assisted self-assembly technique. This method allows for the rapid and efficient formation of discreet macrocyclic units from simple dithiol precursors in high yields with good control over macrocycle size. Up to this point, this technique has been reported on primarily benzylic thiol systems with very little incorporation of endohedral heteroatoms in the resulting assemblies. This study demonstrates the effective incorporation of heterocyclic core molecules allowing for the formation of a more functional cavity, resulting in the formation and crystallization of novel furan- and thiophene-based disulfide dimer and trimer macrocycles, respectively, that are isolated from a range of other larger discrete macrocycles that assemble as well. These disulfide macrocycles can be trapped as their more kinetically stable thioether congeners upon sulfur extrusion.