Novel Diels-Alder and Thermal [4+4] Cycloadditions of Corroles

Abstract

Corroles participate in Diels-Alder and in thermal [4+4] cycloaddition reactions with pentacene to yield novel barrelene-fused corroles.

Key words

corroles - Diels-Alder reaction - thermal [4+4] cyclo­addition

References

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Corrole 1 was prepared by following the procedure described in ref. 8.

30

Spectroscopic data for 2: ¹H NMR (300 MHz, CDCl₃): δ = 9.40 (d, 1 H, J = 4.1 Hz, H-18), 8.69 (d, 1 H, J = 4.1 Hz, H-17), 8.75 and 8.53 (2 d, 2 H, J = 4.7 Hz, H-7,8 or H-12,13), 8.60 and 8.41 (2 d, 2 H, J = 4.4 Hz, H-7,8 or H-12,13), 8.08 (s, 2 H, H-2′,14′), 7.70 (s, 2 H, H-7′,9′), 7.68-7.65 and 7.31-7.28 (2 m, 8 H, H-6′,10′,3′,13′ and H-5′,11′,4′,12′), 7.06 (s, 1 H, H-1′), 5.69 (s, 1 H, H-8′). ¹³C NMR (75 MHz, CDCl₃, based on the HSQC and HMBC spectra): δ = 129.5 (C-β), 127.9 (C-β), 127.5 (C-6′,10′,3′,13′), 126.1 (C-5′,11′,4′,12′), 125.8 (C-β), 125.2 (C-β), 123.1 (C-17), 122.8 (C-2′,14′), 122.4 (C-7′,9′), 117.0 (C-18). HRMS-FAB [M]⁺: m/z = 1072.1698 (calcd for C₅₉H₂₃N₄F₁₅: 1072.1683). UV/Vis (CH₂Cl₂): λ_max (log ε) = 411 (5.82), 567 (5.07), 609 nm (4.88).

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Spectroscopic data for 3: ¹H NMR (300 MHz, CDCl₃): δ = 8.66 and 8.43 (2 d, 4 H, J = 4.7 Hz, H-7,13 and H-8,12), 8.39 (s, 4 H, H-2′,14′,7′′,9′′), 7.81 (s, 4 H, H-7′,9′,2′′,14′′), 7.82-7.80 (m, 4 H, H-6′,10′,3′′,13′′), 7.79-7.76 (m, 4 H, H-13′,3′,6′′,10′′), 7.56 (s, 2 H, H-1′,8′′), 7.47-7.39 (m, 8 H, H-4′,12′,5′′,11′′ and H-5′,11′,4′′,12′′), 5.78 (s, 2 H, H-8′,1′′). ¹³C NMR (75 MHz, CDCl₃): δ = 141.7 and 141.6 (C-1′a,7′a,8′a,14′a,1′′a,7′′a,8′′a,14′′a), 138.0 (C-2,3,17,18), 131.9 and 131.8 (C-2′a,6′a,9′a,13′a,2′′a,6′′a,9′′a,13′′a), 128.0 (C-7,13 or C-8,12), 127.7 and 127.5 (C-6′,10′,3′′,13′′), 126.9 (C-7,13 or C-8,12), 126.35 and 126.29 (C-4′,12′,5′′,11′′ and C-5′,11′,4′′,12′′), 122.7 (C-2′,14′,7′′,9′′), 122.6 (C-7′,9′,2′′,14′′), 50.4 (C-1′,8′′), 49.5 (C-8′,1′′). HRMS (ES) [M + H]⁺: m/z = 1349.2747 (calcd for C₈₁H₃₆N₄F₁₅: 1349.2695). UV/Vis (CH₂Cl₂): λ_max (log ε) = 415 (5.14), 573 (4.44), 612 nm (4.23).

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Spectroscopic data for 5: ¹H NMR (300 MHz, CDCl₃): δ = 8.64 (d, 2 H, J = 4.5 Hz, H-7,13 or H-8,12), 8.61 (s, 2 H, H-3,17), 8.47 (d, 2 H, J = 4.5 Hz, H-7,13 or H-8,12), 8.57 (s, 2 H, H-3,17), 8.19 (s, 4 H, H-2′,7′,9′,14′), 7.72-7.69 and 7.28-7.25 (2 m, 8 H, H-3′,6′,10′,13′ and H-4′,5′,11′,12′), 6.68 (s, 2 H, H-1′,8′). ¹³C NMR (75 MHz, CDCl₃, based on the HSQC and HMBC spectra): δ = 138.0 (C-1′a,7′a,8′a,14′), 132.6 (C-2′a,6′a,9′,13′), 127.5 (C-2′,7′,9′,14′), 127.2 (C-3′,6′,10′,13′), 126.0 (C-4′,5′,11′,12′), 125.0 and 124.7 (C-7,13 and C-8,12), 115.6 (C-1′,8′). HRMS-FAB [M + H]⁺: m/z = 1073.1791 (calcd for C₅₉H₂₄N₄F₁₅: 1073.1761). UV/Vis (CH₂Cl₂): λ_max (log ε) = 424 (5.01), 565 (4.07), 615 nm (3.91).

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Examples of thermal [4+4] cycloaddition reactions have been reported in the literature. In some cases [4+4] cycloadditions compete with Diels-Alder reactions. [34-37]