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DOI: 10.1055/s-2006-950278
Synthesis and Thermal Reactivity of Pyrrolidine- and 2-Pyrrolidinone-Fused Cyclic Enediynes
Publication History
Publication Date:
09 October 2006 (online)
Abstract
Various bicyclic enediynes containing pyrrolidine and pyrrolidinone moieties were synthesised. Thermal reactivity studies indicated the lowering of the onset temperature for Bergman cyclisation upon fusion of these heterocyclic systems onto the cyclic enediyne.
Key word
enediynes - pyrrolidines - pyrrolidinones - heterocyclic systems - Bergman cyclisation
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References and Notes
Spectroscopic Data: All new compounds were characterised by spectroscopic and analytical data. Compound 1: 1H NMR: δ = 8.23 (2 H, dd, J o , m = 6.9, 1.9 Hz), 8.00 (2 H, dd, J o , m = 6.9, 1.9 Hz), 7.32-7.07 (4 H, m), 4.68, 4.19 (2 H, ABq, J = 18.8 Hz), 3.78, 3.52 (2 H, ABq, J = 16.6 Hz), 3.49-3.17 (5 H, m), 2.04-1.85 (4 H, m). 13C NMR: δ = 150.0, 143.5, 130.5, 129.8, 128.8, 128.7, 127.9, 126.9, 124.7, 123.9, 90.5, 87.2, 84.0, 82.4, 59.2, 56.0, 50.2, 45.1, 28.2, 23.9. MS (ES+): m/z = 436 [M + H+]. Compound 2: 1H NMR: δ = 8.31 (2 H, dd, J o , m = 7.0, 2.0 Hz), 7.98 (2 H, dd, J o , m = 7.0, 2.0 Hz), 4.62 (2 H, dd, J = 18.6, 6.0 Hz), 4.33 (1 H, m), 4.21 (2 H, dd, J = 18.6,12 Hz), 3.79 (1 H, dd, J = 12.0, 3.4 Hz), 3.44 (1 H, t, J = 2.0 Hz), 2.65-2.37 (2 H, m), 2.27-2.15 (2 H, m). 13C NMR: δ = 174.7, 150.3, 143.4, 130.6, 130.2, 128.9, 128.7, 128.4, 125.9, 124.6, 124.4, 87.2, 86.5, 84.9, 83.7, 54.8, 48.0, 38.0, 32.6, 29.4, 22.1. MS (ES+): m/z = 450 [M+ H+], 263 [M+ - SO2Ar]. Compound 3: δ = 6.43 (1 H, d, J = 10.8 Hz), 5.88-5.79 (2 H, m), 5.28 (1 H, d, J = 15.6 Hz), 4.51-4.42 (2 H, m), 4.12-4.04 (2 H, m), 3.69-3.41 (2 H, m), 2.25-2.14 (1 H, m), 1.97-1.88 (3 H, m). 13C NMR: δ = 121.7, 120.8, 94.7, 93.0, 86.6, 83.4, 67.1, 65.0, 55.5, 54.7, 49.0, 32.0, 30.6, 23.7. MS (ES+): m/z = 170 [M - OH]. Compound 4: 1H NMR (200 MHz, CDCl3): δ = 8.41 (2 H, dd, J = 8.8 Hz), 8.07 (2 H, dd, J = 8.8 Hz), 7.28 (H, m), 4.28 (2 H, s), 3.66 (2 H, s). 1H NMR (200 MHz, DMSO-d 6 ): δ = 8.39 (2 H, d), 8.13 (2 H, dd, J = 8.8 Hz), 7.32 (2 H, m), 4.40 (2 H, s), 3.53 (2 H, s). 13C NMR (50 MHz, CDCl3): δ = 150.3, 142.5, 130.7, 128.7, 124.7, 124.6, 85.7, 84.7, 46.3, 40.0. 13C NMR (50 MHz, DMSO-d 6 ): δ = 150.29, 142.4, 130.5, 129.2, 129.1, 124.9, 104.5, 86.7, 84.9, 45.7. MS (ES+): m/z = 598 [M+ + H2O], 581 [M + H+], 394 [M+ - SO2Ar].