Efficient Synthesis of the Bicyclo[5.3.0]decane System via Ring-Closing Metathesis

Frédéric  Cachoux; Malika  Ibrahim-Ouali; Maurice  Santelli

doi:10.1055/s-2002-35565

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Synlett 2002(12): 1987-1990
DOI: 10.1055/s-2002-35565

LETTER

Efficient Synthesis of the Bicyclo[5.3.0]decane System via Ring-Closing Metathesis

Frédéric Cachoux, Malika Ibrahim-Ouali*, Maurice Santelli*
Laboratoire de Synthèse Organique associé au CNRS (UMR 6009), Faculté des Sciences de Saint Jérôme, 13397 Marseille Cedex 20, France
e-Mail: m.santelli@univ.u-3mrs.fr; e-Mail: m.ibrahim@univ.u-3mrs.fr;

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Publication History

Received 1 August 2002
Publication Date:
20 November 2002 (online)

Abstract
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Abstract

Starting from spiroepoxide 1, divinylcyclopentanyl derivatives possessing an allylic or a propargylic substituent were obtained. The ring closing metathesis reaction of these compounds using the Grubbs’ catalyst provided the corresponding bicyclic compounds in good yields and with a good stereoselectivity.

Key words

divinylcyclopentanes - cyclisation - metathesis - ring closure - bicyclic compounds

References

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8

Representative Procedure for the RCM Reaction: To a solution of 6a,b or 7a,b (0.72 mmol) in dry CH₂Cl₂ (5 mL) was added Cl₂(PCy₃)₂Ru=CHPh (0.036 mmol) under argon. The mixture was stirred at r.t. for 1-3 h (see Table [1] ), concentrated and the residue purified by flash chromatography. Selected data for 8a: Major diastereomer: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.47 (m, 1 H), 1.88 (m, 2 H), 2.16 (m, 1 H), 2.63 (m, 1 H), 2.70 (m, 1 H), 3.39 (d, J = 12.3 Hz, 1 H), 3.86 (dd, J = 2.1, 14.3 Hz, 1 H), 3.90 (d, J = 12.3 Hz, 1 H), 4.30 (dd, J = 6.7, 14.3 Hz, 1 H), 4.95 (m, 2 H), 5.55 (m, 1 H), 5.70 (dt, J = 2.6, 10.6 Hz, 1 H), 5.91 (m, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.4, 29.5, 48.6, 53.0, 68.7, 78.6, 79.9, 115.6, 129.8, 135.3, 138.0. Minor diastereomer: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.45 (m, 1 H), 1.75 (m, 2 H), 2.22 (m, 1 H), 2.40 (m, 1 H), 2.78 (m, 1 H), 3.55 (d, J = 12.1 Hz, 1 H), 3.61 (d, J = 12.1 Hz, 1 H), 4.21 (dd, J = 2.4, 17.4 Hz, 1 H), 4.30 (dd, J = 2.4, 17.4 Hz, 1 H), 5.10 (m, 2 H), 5.30 (dd, J = 2.8, 12.2 Hz, 1 H), 5.43 (dd, J = 2.8, 12.2 Hz, 1 H), 5.85 (m, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.3, 32.9, 50.8, 51.5, 71.5, 74.6, 83.9, 116.8, 125.7, 130.4, 137.1. Selected data for 8b: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.44 (m, 1 H), 1.89 (m, 2 H), 2.27 (m, 1 H), 2.35 (m, 1 H), 2.90 (m, 1 H), 3.25 (d, J = 14.4 Hz, 1 H), 3.85 (dd, J = 1.7, 18.1 Hz, 1 H), 4.24 (dd, J = 14.4 Hz, 1 H), 4.30 (dd, J = 1.7, 18.1 Hz, 1 H), 5.05 (m, 2 H), 5.13 (s, 1 H), 5.20 (ddd, J = 3.1, 6.2, 11.7 Hz, 1 H), 5.43 (dd, J = 1.7, 11.7 Hz, 1 H), 6.02 (m, 1 H), 7.41 (m, 5 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.8, 30.9, 48.5, 52.4, 53.4, 55.8, 88.2, 116.0, 124.2, 127.8, 128.9, 130.7, 134.9, 135.6, 137.8, 173.4; HRMS (EI) calcd for C₁₈H₂₁NO₂ (M⁺): 284.1651. Found: 284.1670. Selected data for 9a: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.75 (m, 3 H), 2.15 (m, 2 H), 2.40 (m, 1 H), 2.90 (m, 1 H), 3.58 (q, J = 4 Hz, 2 H), 4.48 (q, J = 5 Hz, 2 H), 4.90 (m, 2 H), 5.09 (m, 2 H), 5.58 (d, J = 2 Hz, 2 H), 5.85 (m, 1 H), 6.18 (dd, J = 4, 6 Hz, 2 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.3, 33.0, 50.9, 51.0, 70.9, 75.0, 84.4, 111.1, 117.2, 134.5, 136.8, 138.6; HRMS (EI) calcd for C₁₃H₁₈O₂ (M⁺): 206.1300. Found: 206.1302. Selected data for 9b: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.52 (m, 2 H), 1.90 (m, 2 H), 2.35 (m, 1 H), 3.15 (m, 1 H), 4.24 (m, 1 H), 4.90 (m, 1 H), 6.05 (m, 2 H), 7.18 (m, 5 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.7, 30.9, 48.5, 52.3, 52.5, 55.9, 60.5, 88.3, 111.7, 116.2, 127.4, 128.7, 130.4, 133.4, 134.9, 137.6, 138.7, 173.4; HRMS (EI) calcd for C₂₀H₂₃NO₂ (M⁺): 309.1700. Found: 309.1704. Selected data for 11: Major diastereomer: Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.65 (m, 1 H), 1.82 (m, 2 H), 2.00 (m, 1 H), 2.24 (m, 1 H), 2.72 (m, 1 H), 3.04 (m, 1 H), 3.55 (dd, J = 2.1, 14.3 Hz, 1 H), 3.67 (m, 1 H), 4.20 (m, 1 H), 5.16 (m, 2 H), 5.82 (m, 3 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.6, 31.4, 50.1, 54.8, 56.1, 58.9, 81.2, 119.5, 120.1, 135.1, 143.2. Selected data for 12: Minor diastereomer: Colorless oil; ¹H NMR (400 MHz, CDCl₃):
δ = 1.88 (m, 2 H), 2.19 (m, 2 H), 2.69 (m, 1 H), 2.85 (m,
1 H), 3.29 (m, 1 H), 3.63 (m, 1 H), 3.81 (m, 1 H), 4.08 (m,
1 H), 5.10 (m, 2 H), 5.56 (m, 1 H), 5.87 (m, 2 H); ¹³C NMR (100 MHz, CDCl₃): δ = 29.8, 30.8, 47.9, 53.7, 57.7, 64.6, 81.5, 118.0, 120.4, 137.1, 140.4.