A Cyclocarbonylation for the Synthesis of Bicyclic 3-Methylene-1-phthal­imidoylbutyrolactams from Allene-hydrazones Mediated by Mo(CO)₆

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.

allenes - carbonylation - cyclizations - hydrazones - ­molybdenum

References and Notes

1a For general discussions, see: Transition Metals for Organic Synthesis   Vol. I:  Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. 

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5 Mandai T. In Modern Allene Chemistry   Vol. 2:  Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.925-972  

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12

The crystallographic data for the structure of 4b has been deposited at the Cambridge Crystallographic Data Centre (CCDC 645332).

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4a: 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.