Synlett 2004(10): 1695-1698  
DOI: 10.1055/s-2004-830849
LETTER
© Georg Thieme Verlag Stuttgart · New York

Intramolecular Cyclocarbonylation of Cyclopropylidenyl Aldehydes Mediated by Molybdenum Carbonyl Complex

Chan-Mo Yu*, Young-Taek Hong, Seok-Keun Yoon, Joon-Hwan Lee
Department of Chemistry and Lab for Metal-Catalyzed Reactions (NRL), Sungkyunkwan University, Suwon 440-746, Korea
Fax: +82(31)2907075; e-Mail: cmyu@chem.skku.ac.kr;
Further Information

Publication History

Received 9 April 2004
Publication Date:
15 July 2004 (online)

Abstract

A novel procedure for the synthesis of cis-bicyclic spirocyclopropanelactones from cyclopropylidenyl aldehydes via the molybdenum-mediated cyclocarbonylation is described. The use of (C7H8)Mo(CO)3 with DMSO to promote the reaction results in an efficient and convenient protocol for the three-component assembly in high yields.

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General Procedure: A flame-dried sealed tube containing C7H8Mo(CO)3 (152.0 mg, 0.56 mmol) was evacuated and carefully purged with argon three times and then charged with 3a (103.0 mg, 0.37 mmol) in dry toluene (3 mL). Freshly distilled DMSO (0.27 mL, 289 mg, 3.80 mmol) was then added at 20 °C. After stirring at 20 °C for 1 h, the reaction mixture was heated and allowed to proceed at 90 °C for 5 h. The resulting mixture was treated with EtOAc. The combined organics were washed with H2O (3 ×) and brine (1 ×). The organic layer was dried over anhyd MgSO4, filtered, and concentrated under reduced pressure. The crude product was purified by flash column chromatography (EtOAc-hexane, 1:1) to give 4a (83.0 mg, 0.27 mmol, 73%) as a colorless oil: Rf = 0.37 (EtOAc-hexane, 1:1).

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1H NMR and 13C NMR data: Compound 4a: 1H NMR (500 MHz, CDCl3): δ = 1.03 (dt, 2 H, J = 3.1, 5.6 Hz), 1.31 (dt, 2 H, J = 3.1, 8.2 Hz), 2.45 (s, 3 H), 2.82 (ddd, 1 H, J = 3.9, 8.2, 7.6 Hz), 3.06 (dd, 1 H, J = 7.6, 10.4 Hz), 3.19 (dd, 1 H, J = 3.9, 10.4 Hz), 3.22 (dd, 1 H, J = 5.3, 11.5 Hz), 3.61 (d, 1 H, J = 11.5 Hz), 5.06 (ddd, 1 H, J = 0.6, 5.3, 8.2 Hz), 7.35 (d, 2 H, J = 8.2 Hz), 7.69 (d, 2 H, J = 8.2 Hz). 13C NMR (125 MHz, CDCl3): δ = 178.6, 144.6, 132.1, 130.1, 128.2, 79.7, 54.6, 52.3, 44.1, 24.8, 21.8, 18.4, 13.0. Compound 4b: 1H NMR (500 MHz, CDCl3): δ = 1.29 (d, 3 H, J = 6.7 Hz), 2.42 (s, 3 H), 2.42 (dd, 1 H, J = 3.7, 6.8 Hz), 3.73 (dq, 1 H, J = 3.7, 6.7 Hz), 3.74 (dd, 1 H, J = 4.5, 13.2 Hz), 3.86 (dd, 1 H, J = 0.8, 13.2 Hz), 5.01 (ddd, 1 H, J = 0.8, 4.5, 6.8 Hz), 7.30 (d, 2 H, J = 8.2 Hz), 7.70 (d, 2 H, J = 8.2 Hz). 13C NMR (125 MHz, CDCl3): δ = 177.8, 144.3, 135.6, 130.1, 127.4, 80.3, 61.2, 53.3, 53.1, 25.4, 22.0, 21.8, 18.6, 12.2. Compound 4c: 1H NMR (500 MHz, CDCl3): δ = 0.83 (ddd, 1 H, J = 4.5, 7.3, 9.6 Hz), 1.03 (s, 3 H), 1.06 (ddd, 1 H, J = 4.5, 7.3, 10.1 Hz), 1.11 (ddd, 1 H, J = 4.5, 7.3, 9.6 Hz), 1.31 (ddd, 1 H, J = 4.5, 7.3, 10.1 Hz), 2.45 (s, 3 H), 2.97 (d, 1 H, J = 10.1 Hz), 3.09 (d, 1 H, J = 10.1 Hz), 3.45 (dd, 1 H, J = 1.7, 11.9 Hz), 3.58 (dd, 1 H, J = 5.3, 11.9 Hz), 4.56 (dd, 1 H, J = 1.7, 5.3 Hz), 7.35 (d, 2 H, J = 8.2 Hz), 7.68 (d, 2 H, J = 8.2 Hz). 13C NMR (125 MHz, CDCl3): δ = 178.4, 144.5, 132.6, 130.1, 128.0, 86.2, 58.4, 53.7, 47.4, 28.9, 21.8, 20.6, 14.0, 12.3. Compound 4d: (major) 1H NMR (500 MHz, CDCl3): δ = 0.99 (m, 1 H), 1.05 (m, 2 H), 1.33 (m, 1 H), 1.45 (d, 3 H, J = 6.8 Hz), 2.44 (s, 3 H), 2.84 (ddd, 1 H, J = 5.6, 6.2, 7.9 Hz), 3.37 (dd, 1 H, J = 4.5, 7.9 Hz), 3.40 (dd, 1 H, J = 4.5, 6.2 Hz), 4.13 (dq, 1 H, J = 6.2, 7.3 Hz), 4.87 (dd, 1 H, J = 5.6, 7.3 Hz), 7.34 (d, 2 H, J = 8.2 Hz), 7.71 (d, 2 H, J = 8.2 Hz). 13C NMR (125 MHz, CDCl3): δ = 178.7, 144.4, 133.7, 130.1, 127.5, 86.5, 62.1, 51.6, 43.6, 25.6, 21.8, 18.7, 17.9, 12.1. Compound 4d (minor) 1H NMR (500 MHz, CDCl3): δ = 0.88 (m, 1 H), 1.05 (m, 2 H), 1.18 (m, 1 H), 1.37 (d, 3 H, J = 6.7 Hz), 2.42 (s, 3 H), 2.63 (ddd, 1 H, J = 5.1, 6.5, 7.9 Hz), 3.19 (dd, 1 H, J = 7.9, 11.0 Hz), 3.20 (dd, 1 H, J = 5.1, 11.0 Hz), 3.68 (dq, 1 H, J = 6.7, 11.0 Hz), 4.66 (dd, 1 H, J = 6.5, 11.0 Hz), 7.31 (d, 2 H, J = 8.2 Hz), 7.69 (d, 2 H, J = 8.2 Hz). 13C NMR (125 MHz, CDCl3): δ = 177.7, 144.3, 135.1, 130.1, 128.0, 82.8, 60.2, 52.6, 42.0, 24.9, 21.8, 18.2, 15.2, 12.8. Compound 4e: 1H NMR (500 MHz, CDCl3): δ = 1.05 (m, 2 H), 1.25 (t, 3 H, J = 7.0 Hz), 1.26 (t, 3 H, J = 7.0 Hz), 1.27 (m, 1 H), 1.35 (m, 1 H), 2.24 (dd, 1 H, J = 9.3, 13.8 Hz), 2.43 (dd, 1 H, J = 6.2, 13.8 Hz), 2.66 (dd, 1 H, J = 2.5, 14.9 Hz), 2.72 (dd, 1 H, J = 5.9, 14.9 Hz), 2.76 (ddd, 1 H, J = 6.2, 7.0, 9.3 Hz), 5.11 (ddd, 1 H, J = 2.5, 5.9, 7.0 Hz), 4.18 (q, 2 H, J = 7.0 Hz), 4.20 (q, 2 H, J = 7.0 Hz). 13C NMR (125 MHz, CDCl3): δ = 179.5, 171.4, 170.7, 82.4, 62.2, 60.6, 44.8, 41.3, 38.7, 26.5, 18.9, 14.2, 12.7.