Nontemplated versus Templated Synthesis of a 56-Membered Macrocycle

Markus Albrecht; null Yeni; Roland Fröhlich

doi:10.1055/s-2007-985560

LETTER

Nontemplated versus Templated Synthesis of a 56-Membered Macrocycle

Markus Albrecht*^a, Yeni^a, Roland Fröhlich^b
^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

Abstract

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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

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Referenzen

References and Notes

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9a

Characterization of 1
Mp 198 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.58 (d, ³ J = 8.5 Hz, 4 H, H_ar), 7.53 (d, ³ J = 8.5 Hz, 4 H, H_ar), 7.49 (d, ³ J = 8.8 Hz, 4 H, H_ar), 7.15 (s, 2 H, H_ar), 6.92 (d, ³ J = 8.8 Hz, 4 H, H_ar), 5.86 (ddt, ³ J _trans = 17.0 Hz, ³ J _cis = 10.4 Hz, ³ J = 6.7 Hz, 2 H, HC=), 5.12 (dm, ³ J _trans = 17.0 Hz, 2 H, =CH_trans), 5.05 (dm, ³ J _cis = 10.4 Hz, 2 H, =CH_cis), 4.00 (t, ³ J = 6.7, 4 H, CH₂), 2.51 (q, ³ J = 6.7, 4 H, CH₂), 1.28 (s, 9 H, t-Bu). ¹³C NMR (100 MHz, CDCl₃): δ = 158.5 (C), 141.7 (C), 139.7 (C), 138.3 (C), 137,5 (C), 134.4 (CH), 133.2 (C), 129.8 (CH), 128.0 (CH), 127.8 (C), 127.0 (CH), 126.9 (CH), 117.1 (CH₂), 114.9 (CH), 67.4 (CH₂), 34.2 (C), 33.8 (CH₂), 31.7 (CH₃). MS (EI, 70 eV): m/z (%) = 593.3 (100) [M⁺, C₄₂H₄₃NO₂ ⁺], 578.2 (97), 538.2 (3), 523.2 (12). Anal. Calcd for C₄₂H₄₃NO₂·0.5 H₂O: C, 83.68; H, 7.36; N, 2.32. Found: C, 83.76; H, 7.35; N, 2.11. X-ray crystal structure analysis for 1: formula C₄₂H₄₃NO₂, M = 593.77, colorless crystal 0.30 ¥ 0.10 ¥ 0.10 mm, a = 9.656(1), b = 35.774(1), c = 9.666(1) Å, V = 3339.0(5) Å³, ρ _calc = 1.181 g cm^-3, µ = 0.549 mm^-1, empirical absorption correction (0.853 £ T £ 0.947), Z = 4, orthorhombic, space group Pnma (No. 62), λ = 1.54178 Å, T = 223 K, w and j scans, 13160 reflections collected (h, k, l), [(sinq)/l] = 0.60 Å^-1, 2693 independent (R _int = 0.047) and 2683 observed reflections [I £ 2 s(I)], 215 refined parameters, R = 0.081, wR ² = 0.246, max. residual electron density 0.35 (-0.20) e Å^-3, hydrogen atoms are calculated and refined riding.
Data set was collected with a Nonius KappaCCD diffractometer. Programs used: data collection COLLECT (Nonius B.V., 1998), data reduction Denzo-SMN,^9b absorption correction Denzo,^9c structure solution SHELXS-97,^9d structure refinement SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997), graphics SCHAKAL (E. Keller, Universität Freiburg, 1997).
CCDC 649216 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033, E-mail: deposit@ccdc.cam.ac.uk].

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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, H_ar), 7.49-7.40 (m, 16 H, H_ar), 7.12 (s, 4 H, H_ar), 6.86 (d, ³ J = 8.7 Hz, 8 H, H_ar), 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.