This account details the synthesis of two scyphostatin analogues exhibiting a reactive polar epoxycyclohexenone core and various amide side chains outfitted for late-stage chemical derivatization into the desirable lipophilic tails. Our efforts highlight a key ipso-dearomatization process and provide new insights regarding the incompatibility and orthogonal reactivity of scyphostatin’s functional groups. We further showcase the utility of resorcinol derived 2,5-cyclohexadienones as synthetic platforms capable of participating in selective chemical reactivity, and we further demonstrate their potential for rapid elaboration into complex structural motifs.
Base-promoted intramolecular hydroalkylation of the carbon−carbon triple bond in the ruthenium
bis(arene) complexes [(p-cymene)Ru(η
6-C6H5C⋮CR)][OTf]2 (1, R = Et; 2, R = Ph; OTf = O3SCF3) generates
the strained [3]ruthenocyclophane complexes 3 and 4,
in which a propenyl (−CH2CRCH−) group bridges the
two arene ligands. The presence of the propenyl bridge
results in a bent-metallocene structure for the [3]ruthenocyclophane cation in 4, with an angle of 11.8°
between the arene ligands.
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