On the Functionalization of [2.2](1,4)Phenanthrenoparacyclophane

• Published in: European Journal of Organic Chemistry Vol. 2007; no. 12; pp. 1891 - 1904
• Main Authors: Hopf, Henning, Hucker, Joachim, Ernst, Ludger
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.04.2007; WILEY‐VCH Verlag; Wiley
• Subjects: Chemistry; Chemistry, Organic; Cyclophanes; Heterophanes; o-Quinones; Photocyclization; Physical Sciences; Science & Technology; Stilbenes; stilbenes; SUBSTITUTION; REGIOSELECTIVE HECK ARYLATION; MECHANISM; COMPLEXES; COPPER; OXIDATIVE ADDITION; heterophanes; CROSS-COUPLING REACTIONS; cyclophanes; LIGANDS; ARYL HALIDES; o-quinones; STILLE REACTION; photocyclization
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200601129

Two routes for preparing functionalized [2.2](1,4)phenanthrenoparacyclophanes are described: either the parent system 2 is subjected to electrophilic substitution (bromination, Friedel–Crafts acylation, Rieche formylation: preparation of 5, 6, 7, 11 and 12) or the desired substituents are incorporated in the early stages of the synthesis by the preparation of the corresponding functionalized styryl paracyclophanes and their photocyclization to the respective phenanthrenocyclophanes. By these specific routes various bromides (22a,b), ethers (28a–c) and phenols (29a,b) were synthesized. The latter derivatives, on oxidation, furnish para‐ (31) and ortho‐quinonophanes (30, 32, 33), useful substrates for the preparation of cyclophanes containing phenazine subunits (36). The stilbene → phenanthrene photocyclization can also be employed for the preparation of benzothiophenophanes, e.g. 43 and 44, from the respective precursors. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)