Sterically Congested Chiral 7,8‐Dioxa[6]helicene and Its Dihydro Analogues: Synthesis, Regioselective Functionalization, and Unexpected Domino Prins Reaction

A C2-symmetric 7,8-dioxa[6]helicene-2,13-diol was synthesized from readily available 2,7-dihydroxynaphthalene on a gram scale. A high-yielding synthetic strategy for the regioselective hydroxymethylation at the sterically most hindered C1 position of diol analogues was investigated. The dioxa[6]helicene backbone with configurationally stable helical enantiomers was synthesized, and these enantiomers were separated by HPLC on a chiral stationary phase. We also observed an unexpected domino Prins reaction. This is the first report of a domino Prins reaction occurring on a helicene. Along with the high-yielding regioselective functionalization of dioxa[6]helicene analogues, the synthesis of a few cis-7a,14c-dihydro-functionalized helicenoid diols substituted at the sterically most hindered C1 and C14 positions in their racemic forms was explored.

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