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

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.

divinylcyclopentanes - cyclisation - metathesis - ring closure - bicyclic compounds

References

<A NAME="RG21102ST-1">1</A> Ojima I. Tzamarioudaki M. Li Z. Donovan RJ. Chem. Rev.  1996,  96:  635 

<A NAME="RG21102ST-2A">2a</A> Grubbs RH. Miller SJ. Fu GC. Acc. Chem. Res.  1995,  28:  446 

<A NAME="RG21102ST-2B">2b</A> Schmalz HG. Angew. Chem., Int. Ed. Engl.  1995,  34:  1833 

<A NAME="RG21102ST-2C">2c</A> Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3012 

<A NAME="RG21102ST-2D">2d</A> Mori M. J. Synth. Org. Chem. Jpn.  1998,  56:  115 

<A NAME="RG21102ST-2E">2e</A> Kitamura T. Mori M. Org. Lett.  2001,  3:  1161 

<A NAME="RG21102ST-2F">2f</A> Mori M. Kitamura T. Sato Y. Synthesis  2001,  654 

<A NAME="RG21102ST-2G">2g</A> Saito N. Sato Y. Mori M. Org. Lett.  2002,  4:  803 

<A NAME="RG21102ST-3A">3a</A> Nicolaou KC. Postema MHD. Yue EW. Nadin A. J. Am. Chem. Soc.  1996,  118:  10335 

<A NAME="RG21102ST-3B">3b</A> Yang Z. He Y. Vourloumis D. Vallberg H. Nicolaou KC. Angew. Chem., Int. Ed. Engl.  1997,  36:  166 

<A NAME="RG21102ST-3C">3c</A> 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 

<A NAME="RG21102ST-3D">3d</A> Fürstner A. Langemann K. J. Org. Chem.  1996,  61:  3942 

<A NAME="RG21102ST-3E">3e</A> Fürstner A. Kindler N. Tetrahedron Lett.  1996,  37:  7005 

<A NAME="RG21102ST-3F">3f</A> Crimmins MT. King BW. J. Org. Chem.  1996,  61:  4192 

<A NAME="RG21102ST-3G">3g</A> König B. Horn C. Synlett  1996,  1013 

<A NAME="RG21102ST-3H">3h</A> Clark TD. Ghadiri MR. J. Am. Chem. Soc.  1995,  117:  12364 

<A NAME="RG21102ST-3I">3i</A> Schwab P. France MB. Ziller JW. Grubbs RH. Angew. Chem., Int. Ed. Engl.  1995,  34:  2039 

<A NAME="RG21102ST-3J">3j</A> Mori M. Sakakibara N. Kinoshita A. J. Org. Chem.  1998,  63:  6082 

<A NAME="RG21102ST-3K">3k</A> Trnka T.-M. Grubbs R.-H. Acc. Chem. Res.  2001,  34:  18 

<A NAME="RG21102ST-3L">3l</A> Kadota I. Ohno A. Matsuda K. Yamamoto Y. J. Am. Chem. Soc.  2002,  124:  3562 

<A NAME="RG21102ST-3M">3m</A> Fürstner A. Radkowski K. Wirtz C. Goddard R. Lehmann C.-W. Mynott R. J. Am. Chem. Soc.  2002,  124:  7061 

<A NAME="RG21102ST-3N">3n</A> 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 

<A NAME="RG21102ST-4">4</A> Cachoux F. Ibrahim-Ouali M. Santelli M. Tetrahedron Lett.  2000,  41:  1767 

<A NAME="RG21102ST-5">5</A> Cachoux F. Ibrahim-Ouali M. Santelli M. Synlett  2000,  418 

<A NAME="RG21102ST-6">6</A> Cachoux F. Ibrahim-Ouali M. Santelli M. Synth. Commun.  2001,  31:  31 

<A NAME="RG21102ST-7">7</A> Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 

<A NAME="RG21102ST-8">8</A>

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.

<A NAME="RG21102ST-9">9</A> Hérisson JL. Chauvin Y. Makromol. Chem.  1970,  141:  161 

<A NAME="RG21102ST-10A">10a</A> Armstrong SK. Christie BA. Tetrahedron Lett.  1996,  37:  9373 

<A NAME="RG21102ST-10B">10b</A> Shon Y.-S. Lee TR. Tetrahedron Lett.  1997,  38:  1283 

<A NAME="RG21102ST-10C">10c</A> Fürstner A. Seidel G. Kindler N. Tetrahedron Lett.  1999,  55:  8215 

<A NAME="RG21102ST-11A">11a</A> Iwama T. Matsumoto H. Shimizu H. Kataoka O. Tanabe G. J. Chem. Soc., Perkin Trans. 1  1998,  1569 

<A NAME="RG21102ST-11B">11b</A> Stoodley RJ. Wilkins RB. J. Chem. Soc., Perkin Trans. 1  1974,  1572