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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Publikationsverlauf

Received 1 August 2002
Publikationsdatum:
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

1 Ojima I. Tzamarioudaki M. Li Z. Donovan RJ. Chem. Rev. 1996, 96: 635

Google Scholar
2a Grubbs RH. Miller SJ. Fu GC. Acc. Chem. Res. 1995, 28: 446

Crossref Google Scholar
2b Schmalz HG. Angew. Chem., Int. Ed. Engl. 1995, 34: 1833

Crossref Google Scholar
2c Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012

Crossref Google Scholar
2d Mori M. J. Synth. Org. Chem. Jpn. 1998, 56: 115

Crossref Google Scholar
2e Kitamura T. Mori M. Org. Lett. 2001, 3: 1161

Crossref Google Scholar
2f Mori M. Kitamura T. Sato Y. Synthesis 2001, 654

Crossref Google Scholar
2g Saito N. Sato Y. Mori M. Org. Lett. 2002, 4: 803

Crossref Google Scholar
3a Nicolaou KC. Postema MHD. Yue EW. Nadin A. J. Am. Chem. Soc. 1996, 118: 10335

Crossref Google Scholar
3b Yang Z. He Y. Vourloumis D. Vallberg H. Nicolaou KC. Angew. Chem., Int. Ed. Engl. 1997, 36: 166

Crossref Google Scholar
3c Meng D. Su DS. Balog A. Bertinato P. Sorensen EJ. Danishefsky SJ. Zheng YH. Chou TC. He L. Horwitz SB. J. Am. Chem. Soc. 1997, 119: 2733

Crossref Google Scholar
3d Fürstner A. Langemann K. J. Org. Chem. 1996, 61: 3942

Crossref Google Scholar
3e Fürstner A. Kindler N. Tetrahedron Lett. 1996, 37: 7005

Crossref Google Scholar
3f Crimmins MT. King BW. J. Org. Chem. 1996, 61: 4192

Crossref Google Scholar
3g König B. Horn C. Synlett 1996, 1013

Crossref Google Scholar
3h Clark TD. Ghadiri MR. J. Am. Chem. Soc. 1995, 117: 12364

Crossref Google Scholar
3i Schwab P. France MB. Ziller JW. Grubbs RH. Angew. Chem., Int. Ed. Engl. 1995, 34: 2039

Crossref Google Scholar
3j Mori M. Sakakibara N. Kinoshita A. J. Org. Chem. 1998, 63: 6082

Crossref Google Scholar
3k Trnka T.-M. Grubbs R.-H. Acc. Chem. Res. 2001, 34: 18

Crossref Google Scholar
3l Kadota I. Ohno A. Matsuda K. Yamamoto Y. J. Am. Chem. Soc. 2002, 124: 3562

Crossref Google Scholar
3m Fürstner A. Radkowski K. Wirtz C. Goddard R. Lehmann C.-W. Mynott R. J. Am. Chem. Soc. 2002, 124: 7061

Crossref Google Scholar
3n Humphrey J.-M. Liao Y. Ali A. Rein T. Wong Y.-L. Chen H.-L. Courtney A.-K. Martin S.-F. J. Am. Chem. Soc. 2002, 124: 8584

Crossref Google Scholar
4 Cachoux F. Ibrahim-Ouali M. Santelli M. Tetrahedron Lett. 2000, 41: 1767

Crossref Google Scholar
5 Cachoux F. Ibrahim-Ouali M. Santelli M. Synlett 2000, 418

Artikel in Thieme Connect Google Scholar
6 Cachoux F. Ibrahim-Ouali M. Santelli M. Synth. Commun. 2001, 31: 31

Google Scholar
7 Grubbs RH. Chang S. Tetrahedron 1998, 54: 4413

Crossref Google Scholar
9 Hérisson JL. Chauvin Y. Makromol. Chem. 1970, 141: 161

Google Scholar
10a Armstrong SK. Christie BA. Tetrahedron Lett. 1996, 37: 9373

Crossref Google Scholar
10b Shon Y.-S. Lee TR. Tetrahedron Lett. 1997, 38: 1283

Crossref Google Scholar
10c Fürstner A. Seidel G. Kindler N. Tetrahedron Lett. 1999, 55: 8215

Crossref Google Scholar
11a Iwama T. Matsumoto H. Shimizu H. Kataoka O. Tanabe G. J. Chem. Soc., Perkin Trans. 1 1998, 1569

Crossref Google Scholar
11b Stoodley RJ. Wilkins RB. J. Chem. Soc., Perkin Trans. 1 1974, 1572

Crossref Google Scholar

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.