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Synlett 2007(14): 2295-2297  
DOI: 10.1055/s-2007-985560
LETTER
© Georg Thieme Verlag Stuttgart · New York

Nontemplated versus Templated Synthesis of a 56-Membered Macrocycle

Markus Albrecht*a, Yenia, Roland Fröhlichb
a Institut für Organische Chemie, RWTH Aachen, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092385; e-Mail: markus.albrecht@oc.rwth-aachen.de;
b Organisch-Chemisches Institut, Universität Münster, Corrensstraße 40, 49148 Münster, Germany
Further Information

Publication History

Received 1 June 2007
Publication Date:
24 July 2007 (online)

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Abstract

The amine-substituted quinquephenylene 1 was prepared in a Suzuki coupling approach and by reaction with terephthalic dialdehyde (7) it was transformed into the phenyl-connected diimine 8. Ring-closing metathesis with the Grubbs I or II catalyst led to the corresponding macrocycle 9. Hydrogenation resulted in the reduction of the double bonds as well as the removal of the template to yield the 56-membered macrocycle 6 in an overall yield of 43% (from 1). Direct metathesis reaction of 1 followed by hydrogenation afforded 6 in only 21% yield.

Key words

macrocycles - quinquephenylene - ring-closing meta­thesis - preorganization - template effect

    References and Notes

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    Characterization of 1
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13

Characterization of 6
Mp >250 °C. 1H NMR (300 MHz, CDCl3): δ = 7.53 (d, 3 J = 8.4 Hz, 8 H, Har), 7.49-7.40 (m, 16 H, Har), 7.12 (s, 4 H, Har), 6.86 (d, 3 J = 8.7 Hz, 8 H, Har), 3.98 (t, 3 J = 6.2 Hz, 8 H, CH2), 1.82 (m, 8 H, CH2), 1.53 (m, 8 H, CH2), 1.26 (s, 18 H, t-Bu). 13C NMR (75 MHz, CDCl3): δ = 158.7 (C), 141.0 (C), 139.6 (C), 138.5 (C), 138.4 (C), 133.1 (C), 129.8 (CH), 128.0 (CH), 127.3 (C), 127.0 (CH), 126.6 (CH), 115.0 (CH), 67.5 (CH2), 34.1 (C), 31.6 (CH3), 28.6 (CH2), 25.0 (CH2). ESI-MS (+): m/z = 1135.4 [MH+, C80H82N2O4 + H+]. Anal. Calcd for C80H82N2O4·H2O: C, 83.30; H, 7.34; N, 2.43. Found: C, 83.47; H, 7.37; N, 1.99.