Intramolecular Cyclocarbonylation of Cyclopropylidenyl Aldehydes Mediated by Molybdenum Carbonyl Complex

Chan-Mo Yu; Young-Taek Hong; Seok-Keun Yoon; Joon-Hwan Lee

doi:10.1055/s-2004-830849

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Synlett 2004(10): 1695-1698
DOI: 10.1055/s-2004-830849

LETTER

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;

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Publikationsverlauf

Received 9 April 2004
Publikationsdatum:
15. Juli 2004 (online)

Abstract
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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.

Key words

aldehydes - carbonyl complexes - cyclizations - cyclopropane - molybdenum

References

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15

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: R_f = 0.37 (EtOAc-hexane, 1:1).

16

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.