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. 2021;53(19):3585-3590.
doi: 10.1055/a-1479-6611. Epub 2021 Apr 12.

Synthesis of 2,24-Diene-12,13,15,16,34,35,37,38-octaphenyl[4.4]-triphenylparacyclophane

Bernard Wiredu  1 , Mahendra Thapa  1 , Sheen Y Hua  1 , John Desper  1 , Duy H Hua  1
Affiliations

Synthesis of 2,24-Diene-12,13,15,16,34,35,37,38-octaphenyl[4.4]-triphenylparacyclophane

Bernard Wiredu et al. Synthesis (Stuttg). 2021.

Abstract

A new octaphenyl[4.4]triphenylparacyclophanediene was readily synthesized in six steps from p-xylene via the installment of bromine atoms, replacement with a vinyl group, carbonylative coupling, intermolecular followed by intramolecular double Grubbs olefin metathesis, Knoevenagel condensation, and Diels-Alder cycloaddition. The belt-shaped structure and trans-stereochemistry of the alkene moieties of the octaphenyl[4.4]triphenylparacyclophane and a synthetic intermediate, 2,21-dioxo-11,30-diene[3.4.3.4]paracyclophane, were determined by X-ray crystallography. The synthetic methodology leading to octaphenyl[4.4]triphenylparacyclophane is applicable for the synthesis of substituted triphenylparacyclophanes and possibly their corresponding bis-hexabenzocoronenylparacyclophanes via a Scholl-Mullen oxidative aryl-aryl coupling reaction.

Keywords: Diels–Alder cycloaddition; Grubbs olefin metathesis; Knoevenagel condensation; belt-shaped molecules; carbonylative coupling; cyclophanes; octaphenyl[4.4]-triphenylparacyclophane.

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Conflict of interest statement

Conflict of Interest The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Retrosynthesis of cyclophane 1
Figure 2
Figure 2
ORTEP drawing of the single-crystal X-ray analysis of diketone cyclophane 3; CCDC 2065344. Selected bond lengths (Å) and angles (°): C1–C2 1.5171(14), C2–C3 1.5226(14), C2–O2 1.2090(12), C1–C17 1.5183(14), C7–C10 1.5182(14), C10–C11 1.5023(15), C11–C12 1.3336(15), C14–C15 1.3976(14); C1–C2–C3 116.51(8), C3–C4–C5 120.71(9), C1–C2–O2 122.15(9), C6–C7–C10 120.63(9), C7–C10–C11 112.66(9), C10–C11–C12 124.34(10), C11–C12–C13 124.88(10), C14–C15–C16 121.24(9).
Figure 3
Figure 3
ORTEP drawing of the single-crystal X-ray analysis of triphenylparacyclophane 1; CCDC 2065345. Selected bond lengths (Å) and angles (°): C4–C5 1.544(4), C8–C11 1.504(4), C11–C12 1.406(4), C11–C16 1.412(4), C13–C14 1.412(4), C14–C15 1.402(4), C14–C17 1.496(4), C15–C16 1.407(4), C20–C21 1.379(4), C1–C20 1.527(4), C1–C2 1.468(5), C2–C3 1.359(5), C3–C4 1.500(4); C13–C14–C15 120.3(2), C13–C14–C17 119.4(2), C6–C5–C10 117.8(3), C19–C20–C21 117.7(3), C18–C19–C20 121.5(3), C5–C10–C9 121.2(3), C1–C2–C3 125.0(3), C2–C3–C4 122.2(3).
Scheme 1
Scheme 1
Synthesis of 2,24-diene-12,13,15,16,34,35,37,38-octaphenyl[4.4]triphenylparacyclophane (1)
See this image and copyright information in PMC

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