A Short and Efficient Synthesis
of 3-Spiro-α-methylene-γ-butyrolactone Oxindolones
from Isomerised Bromo Derivatives of Morita-Baylis-Hillman Adducts

Ponnusamy Shanmugam; Baby Viswambharan

doi:10.1055/s-0028-1083549

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Synlett 2008(18): 2763-2768
DOI: 10.1055/s-0028-1083549

LETTER

A Short and Efficient Synthesis of 3-Spiro-α-methylene-γ-butyrolactone Oxindolones from Isomerised Bromo Derivatives of Morita-Baylis-Hillman Adducts

Ponnusamy Shanmugam*, Baby Viswambharan
Chemical Sciences and Technology Division, National Institute for Interdisciplinary Science and Technology (NIIST), Thiruvananthapuram 695 019, Kerala, India
Fax: +91(471)2491712; e-Mail: shanmu196@rediffmail.com;

Further Information

Publication History

Received 2 June 2008
Publication Date:
16 October 2008 (online)

Abstract
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Abstract

A short and efficient synthesis of α-methylene-γ-butyrolactone-3-spirooxindolones by the reaction of isomerised bromo derivatives of Morita-Baylis-Hillman adducts of isatin and formaldehyde followed by acid-catalysed lactonisation has been achieved. The oxindolidino allyl bromide has been used for the first time for the allylation of aldehydes to afford a 2-oxindolidino homoallylic alcohol which on acid-catalysed lactonisation delivered the title compounds in excellent yield. Synthetic transformation of the spirolactone oxindole is demonstrated with the preparation of an oxirane derivative and a second Morita-Baylis-Hillman adduct.

Key words

isatin - allylindium - Morita-Baylis-Hillman adduct - lactonisation - spirolactone oxindoles

References and Notes

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34

Typical Procedure: A mixture of isomerised MBH adduct (100 mg), 40% aq formaldehyde (1.2 equiv) and indium powder (1.6 equiv) in DMF (1 mL) was stirred at r.t. for 6 h. After completion (TLC), the reaction was quenched with sat. NH₄Cl and stirred further for half an hour. The resulting crude homoallylic alcohol was extracted with EtOAc, dried and concentrated. The crude homoallylic alcohol compound in benzene (1 mL) was subjected to lactonisation with PTSA (0.2 equiv) under reflux for 30 min. After the completion of the reaction (TLC), PTSA was removed by washing with H₂O. The organic layer was washed with brine, evaporated in vacuo and then purified by silica gel column chromatog-raphy to afford the products (65-85%).
Spectral Data for Selected Compounds: Compound 4: FTIR (CH₂Cl₂): 1613, 1715, 3004 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.65 (s, 3 H), 3.20 (s, 3 H), 3.90 (s, 3 H), 6.79-6.81 (d, 1 H, J = 7.8 Hz), 6.95-7.00 (d, 1 H, J = 7.8 Hz), 7.26-7.31 (d, 2 H, J = 7.8 Hz). MS (FAB): m/z calcd for C₁₃H₁₃NO₃: 231.24; found [M + 1]: 232.38. Compound 5: FTIR (CH₂Cl₂): 1613, 1715, 2995 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.44 (s, 3 H), 3.23 (s, 3 H), 3.96 (s, 3 H), 6.81-6.84 (d, 1 H, J = 7.8 Hz), 7.03-7.08 (d, 1 H, J = 7.8 Hz), 7.29-7.34 (d, 1 H, J = 7.8 Hz), 7.51-7.54 (d, 1 H, J = 7.8 Hz). MS (FAB): m/z calcd for C₁₃H₁₃NO₃: 231.24; found [M + 1]: 232.35. Compound 6: FTIR (CH₂Cl₂): 1115, 1613, 1715, 2920, 3265 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 1.70 (br s, 1 H), 3.30 (s, 3 H), 3.50 (s, 3 H), 3.78-3.81 (d,
1 H, J = 11.4 Hz), 4.13-4.17 (d, 1 H, J = 11.4 Hz), 6.26 (s,
1 H), 6.64 (s, 1 H), 6.88-6.91 (m, 1 H), 7.00-7.05 (m, 2 H), 7.20-7.30 (m, 1 H). MS (FAB): m/z calcd for C₁₄H₁₅NO₄: 261.27; found [M + 1]: 262. 38. Compound 7: FTIR (CH₂Cl₂): 1115, 1613, 1715, 1766, 2920 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ =3.26 (s, 3 H), 4.41-4.44 (d, 1 H, J = 9.3 Hz), 4.68-4.71 (d, 1 H, J = 9.3 Hz), 5.35 (s, 1 H), 6.31 (s, 1 H), 6.91-6.94 (d, 1 H, J = 6.0 Hz), 7.11-7.21 (m, 2 H), 7.36-7.40 (d, 1 H, J = 6.0 Hz). ^¹³C NMR (75 MHz, CDCl₃/TMS): δ = 27.1, 54.5, 73.0, 108.2, 109.2, 109.5, 122.5, 123.2, 130.3, 137.5, 143.8, 168.47, 175.5. MS (FAB): m/z calcd for C₁₃H₁₁NO₃: 229.23; found [M + 1]: 230.3. Compound 18: FTIR (CH₂Cl₂): 1116, 1618, 1720, 1770, 3020 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 2.34 (s,
3 H), 3.20 (s, 3 H), 4.40-4.43 (d, 1 H, J = 9.0 Hz), 4.67-4.70 (d, 1 H, J = 9.0 Hz), 5.36 (s, 1 H), 6.36 (s, 1 H), 6.80-6.82 (d, 1 H, J = 6.0 Hz), 7.01 (s, 1 H), 7.18-7.16 (d, 1 H, J = 6.0 Hz). ^¹³C NMR (75 MHz, CDCl₃/TMS): δ = 20.9, 26.7, 54.3, 72.6, 109.1, 123.7, 124.4, 129.8, 130.6, 133.5, 137.4, 141.0, 168.32, 175.2. MS (FAB): m/z calcd for C₁₄H₁₃NO₃: 243.25; found [M + 1]: 244.3. Compound 19: FTIR (CH₂Cl₂): 1114, 1347, 1610, 1688, 1731, 1770, 2925 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 3.32 (s, 3 H), 4.45-4.48 (d, 1 H, J = 9.0 Hz), 4.69-4.72 (d, 1 H, J = 9.0 Hz), 5.36 (s, 1 H), 6.41 (s, 1 H), 7.07-7.09 (d, 1 H, J = 6.0 Hz), 7.75 (s, 1 H), 7.92-7.94 (d, 1 H, J = 6.0 Hz), 9.91 (s, 1 H). ^¹³C NMR (75 MHz, CDCl₃/TMS): δ = 27.1, 53.9, 72.1, 105.4, 123.6, 125.0, 130.9, 132.74, 133.7, 136.6, 148.9, 167.6, 175.4, 190.1. MS (FAB): m/z calcd for C₁₄H₁₁NO₄: 257.24; found [M + 1]: 258.6. Compound 24: FTIR (CH₂Cl₂): 1613, 1715, 1750, 3004 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 3.20 (s,
3 H), 3.37-3.41 (d, 1 H, J = 12.0 Hz), 3.81-3.85 (d, 1 H, J = 12.0 Hz), 4.25-4.28 (d, 1 H, J = 9.0 Hz), 4.78-4.82 (d, 1 H, J = 9.0 Hz), 6.99-7.02 (d, 1 H, J = 9.0 Hz), 7.14-7.26 (m,
2 H), 7.42-7.47 (t, 1 H, J = 9.0 Hz). MS (FAB): m/z calcd for C₁₃H₁₁NO₄: 245.24; found [M + 1]: 246.38. Compound 25: FTIR (CH₂Cl₂): 1613, 1715, 1750, 3004, 3282 cm^-¹. ^¹H NMR (300 MHz, CDCl₃/TMS): δ = 1.68 (s, 1 H), 3.32 (s,
3 H), 4.45-4.48 (d, 1 H, J = 9.0 Hz), 4.69-4.72 (d, 1 H, J = 9.0 Hz), 5.36 (s, 1 H), 5.58 (s, 1 H), 5.63 (s, 1 H), 6.41 (s,
1 H), 7.06-7.09 (d, 1 H, J = 6.0 Hz), 7.75 (s, 1 H), 7.91-7.96 (d, 1 H, J = 6.0 Hz). MS (FAB): m/z calcd for C₁₇H₁₄N₂O₄: 310.30; found [M + 1]: 311.41.