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DOI: 10.1055/s-2007-985603
A Cyclocarbonylation for the Synthesis of Bicyclic 3-Methylene-1-phthalimidoylbutyrolactams from Allene-hydrazones Mediated by Mo(CO)6
Publication History
Publication Date:
28 August 2007 (online)
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Abstract
A novel carbonylative cyclization for the synthesis of cis-fused bicyclic 3-methylenebutyrolactams from allene-hydrazone functionalities mediated by Mo(CO)6 with DMSO is described. Dramatic solvent effect of CH2Cl2 was observed to expedite the process to afford the cyclized products in good yields.
Key words
allenes - carbonylation - cyclizations - hydrazones - molybdenum
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References and Notes
The crystallographic data for the structure of 4b has been deposited at the Cambridge Crystallographic Data Centre (CCDC 645332).
134a: 1H NMR (500 MHz, CDCl3): δ = 3.57 (dd, J = 4.50, 10.68 Hz, 1 H), 3.71 (m, 1 H), 3.97 (dd, J = 7.31, 8.99 Hz, 1 H), 4.04 (dd, J = 2.81, 8.99 Hz, 1 H), 4.15 (d, J = 10.68 Hz, 1 H), 4.53 (ddd, J = 1.12, 4.50, 7.31 Hz, 1 H), 5.63 (d, J = 2.40 Hz, 1 H), 6.29 (d, J = 2.40 Hz, 1 H), 7.80-7.90 (m, 2 H), 7.91-7.97 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 41.9, 62.9, 71.6, 75.6, 121.6, 124.5, 124.7, 130.1, 130.5, 135.0, 135.1, 139.1, 164.7, 164.9, 165.1. 4b: 1H NMR (500 MHz, CDCl3): δ = 2.44 (s, 3 H), 3.25 (m, 2 H), 3.55 (m, 2 H), 3.66 (m, 1 H), 4.47 (ddd, J = 2.25, 5.62, 8.15 Hz, 1 H), 5.56 (d, J = 2.40 Hz, 1 H), 6.22 (d, J = 2.40 Hz, 1 H), 7.35 (m, 2 H), 7.75 (m, 2 H), 7.82 (m, 2 H), 7.91 (m, 1 H), 7.95 (m, 1 H). 13C NMR (125 MHz, CDCl3): δ = 21.8, 40.2, 52.2, 53.9, 60.7, 122.2, 124.3, 124.7, 128.3, 130.0, 130.1, 130.2, 132.8, 135.1, 135.3, 137.7, 144.4, 164.5, 164.7, 164.9. 4c: 1H NMR (500 MHz, CDCl3): δ = 1.25 (t, J = 7.03 Hz, 6 H), 2.45 (m, 2 H), 2.69 (m, 2 H), 3.69 (m, 1 H), 4.12 (m, 4 H), 4.50 (m, 1 H), 5.57 (d, J = 2.40 Hz, 1 H), 6.63 (d, J = 2.40 Hz, 1 H), 7.80 (m, 2 H), 7.91 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 14.2, 36.7, 40.1, 40.6, 61.0, 61.5, 61.8, 62.1, 62.2, 120.7, 124.1, 124.4, 130.4, 130.7, 135.1, 140.2, 156.6, 164.5, 164.9, 165.2, 170.7, 171.8. 4d: 1H NMR (500 MHz, CDCl3): δ = 1.52 (m, 1 H), 1.73 (m, 1 H), 1.84 (m, 1 H), 1.91 (m, 2 H), 2.02 (m, 1 H), 3.51 (m, 1 H), 4.42 (m, 1 H), 5.54 (d, J = 2.40 Hz, 1 H), 6.20 (d, J = 2.40 Hz, 1 H), 7.80 (m, 2 H), 7.91 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 23.5, 31.4, 35.6, 41.0, 62.9, 116.5, 120.0, 124.2, 124.4, 130.5, 134.1, 135.0, 141.9, 155.3, 165.2, 165.9. 4e: 1H NMR (500 MHz, CDCl3): δ = 1.50 (d, J = 6.30 Hz, 3 H), 2.44 (s, 3 H), 3.30 (m, 1 H), 3.51 (m, 1 H), 3.61 (m, 1 H), 4.12 (m, 1 H), 4.50 (m, 1 H), 5.46 (d, J = 2.40 Hz, 1 H), 6.00 (d, J = 2.40 Hz, 1 H), 7.16-7.35 (m, 2 H), 7.81-7.97 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 16.6, 20.3, 45.3, 51.0, 60.0, 61.7, 116.6, 121.5, 123.5, 124.4, 124.6, 127.7, 128.1, 130.0, 130.1, 134.8, 135.2, 135.4, 136.9, 144.1, 164.9, 164.9. 4f: 1H NMR (500 MHz, CDCl3): δ = 1.48 (s, 3 H), 2.45 (s, 3 H), 3.03 (m, 1 H), 3.10 (m, 2 H), 3.63 (m, 2 H), 5.53 (d, J = 2.40 Hz, 1 H), 6.20 (m, 1 H), 7.27-7.43 (m, 2 H), 7.65-7.97 (m, 6 H). 13C NMR (125 MHz, CDCl3): δ = 21.9, 23.7, 47.7, 54.3, 58.0, 68.8, 122.1, 124.5, 124.6, 128.3, 130.1, 130.2, 132.2, 135.3, 135.4, 138.0, 144.4, 163.8, 165.4, 165.5. 4g: 1H NMR (500 MHz, CDCl3): δ = 1.85 (dq, J = 2.9, 14.7 Hz, 1 H), 2.04 (m, 1 H), 2.45 (s, 3 H), 2.61 (dd, J = 10.7, 12.7 Hz, 1 H), 2.94 (ddd, J = 2.9, 11.7, 11.7 Hz, 1 H), 3.41 (m, 1 H), 3.55 (m, 1 H), 3.75 (ddd, J = 2.0, 6.8, 12.7 Hz, 1 H), 4.15 (m, 1 H), 5.62 (s, 1 H), 6.24 (s, 1 H), 7.35 (d, J = 7.8 Hz, 2 H), 7.66 (d, J = 7.8 Hz, 2 H), 7.80 (m, 2 H), 7.88 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 25.3, 29.9, 36.9, 41.3, 46.7, 54.2, 121.7, 124.1, 124.4, 124.4, 127.4, 127.7, 130.0, 130.0, 130.3, 133.9, 135.0, 135.2, 137.7, 144.2, 164.6, 165.4, 166.4.