Cobalt Carbonyl-Catalyzed Tandem [2+2+1]/[4+2] Cycloaddition of Dienediyne to New Tetracycles

Do Han Kim; Young Keun Chung

doi:10.1055/s-2005-871578

LETTER

Cobalt Carbonyl-Catalyzed Tandem [2+2+1]/[4+2] Cycloaddition of Dienediyne to New Tetracycles

Do Han Kim, Young Keun Chung*
Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747, Korea
Fax: +82(2)8890310; e-Mail: ykchung@snu.ac.kr;

Abstract

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Abstract

A tandem reaction of dienediynes catalyzed by dicobalt octacarbonyl gives teracyclic compounds in a poor to high yield depending upon the substrate. The structural frame of the synthesized polycyclic compounds is disclosed for the first time in this study.

Key words

carbonylation - cyclization - enone - polycycle - tandem reaction

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References

For recent reviews, see:

<A NAME="RU09505ST-1A">1a</A> Carreno MC. Urbano A. Synlett 2005, 1

<A NAME="RU09505ST-1B">1b</A> Rodríguez Rivero M. Adrio J. Carretero JC. Synlett 2005, 26

<A NAME="RU09505ST-1C">1c</A> France S. Weatherwax A. Taggi AE. Lectka T. Acc. Chem. Res. 2004, 37: 592

<A NAME="RU09505ST-1D">1d</A> Harvey RG. Curr. Org. Chem. 2004, 8: 303

<A NAME="RU09505ST-1E">1e</A> Denissova I. Barriault L. Tetrahedron 2003, 59: 10105

For recent reviews, see:

<A NAME="RU09505ST-2A">2a</A> Bolm C. Legros J. Le Paih J. Zani L. Chem. Rev. 2004, 104: 6217

<A NAME="RU09505ST-2B">2b</A> Montgomery J. Angew. Chem. Int. Ed. 2004, 43: 3890

<A NAME="RU09505ST-2C">2c</A> Zeni G. Larock RC. Chem. Rev. 2004, 104: 2285

<A NAME="RU09505ST-2D">2d</A> Nakamura I. Yamamoto Y. Chem. Rev. 2004, 104: 2127

<A NAME="RU09505ST-2E">2e</A> Varela JA. Saa C. Chem. Rev. 2003, 103: 3787

<A NAME="RU09505ST-3A">3a</A> Ajamian A. Gleason L. Angew. Chem. Int. Ed. 2004, 43: 3754

<A NAME="RU09505ST-3B">3b</A> Lee JM. Na Y. Han H. Chang S. Chem. Soc. Rev. 2004, 33: 302

<A NAME="RU09505ST-3C">3c</A> Fogg DE. dos Santos EN. Coord. Chem. Rev. 2004, 248: 2365

<A NAME="RU09505ST-3D">3d</A> Wasilke J.-C. Obrey SJ. Baker RT. Bazan GC. Chem. Rev. 2005, 105: in press

<A NAME="RU09505ST-3E">3e</A> Ramon DJ. Yus M. Angew. Chem. Int. Ed. 2005, 44: 1602

<A NAME="RU09505ST-4">4</A> Wender PA. Gamber G. Hubbard RD. Pham SM. Zhang L. J. Am. Chem. Soc. 2005, in press; and references therein

<A NAME="RU09505ST-5">5</A> Kim DH. Chung YK. Chem. Commun. 2005, 1634

<A NAME="RU09505ST-6A">6a</A> Son SU. Park KH. Lee SJ. Kim BM. Chung YK. Synlett 2003, 1101

<A NAME="RU09505ST-6B">6b</A> Kim DH. Son SU. Chung YK. Lee S.-G. Chem. Commun. 2002, 56

<A NAME="RU09505ST-6C">6c</A> Son SU. Yoon YA. Choi DS. Park JK. Kim BM. Org. Lett. 2001, 3: 1065

<A NAME="RU09505ST-6D">6d</A> Son SU. Chung YK. Lee SG. J. Org. Chem. 2000, 65: 6142

<A NAME="RU09505ST-6E">6e</A> Son SU. Choi DS. Chung YK. Org. Lett. 2000, 2: 2097

<A NAME="RU09505ST-6F">6f</A> Hong SH. Choi DS. Chung YK. Lee S. Chem. Commun. 1999, 2099

Compound 1d: yield 59%. ¹H NMR (CDCl₃): δ = 6.22 (dd, J = 10.4, 15.1 Hz, 1 H), 6.06 (dd, 10.6, 14.9 Hz, 1 H), 5.70 (m, 1 H), 5.54 (m, 1 H), 4.10 (t, J = 2.1 Hz, 2 H), 4.04 (d, J = 6.4 Hz, 2 H), 2.36 (tt, J = 2.1, 7.0 Hz, 2 H), 2.30 (dd, J = 2.6, 7.0 Hz, 2 H), 1.97 (t, J = 2.6 Hz, 1 H), 1.75 (d, J = 6.6 Hz, 2 H), 1.73 (t, J = 7.0 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.0, 130.8, 130.3, 126.0, 85.6, 83.5, 76.8, 69.9, 69.0, 57.4, 27.5, 18.2, 17.8, 17.6. HRMS: m/z calcd for C₁₄H₁₈O₁: 202.1358; found: 202.1353.
Compound 2d: yield 63%. ¹H NMR (CDCl₃): δ = 6.23 (dd, J = 10.4, 15.1 Hz, 1 H), 6.06 (dd, 10.6, 14.8 Hz, 1 H), 5.73 (m, 1 H), 5.61 (m, 1 H), 4.13 (t, J = 1.9 Hz, 2 H), 4.07 (d, J = 6.4 Hz, 2 H), 3.38-3.34 (m, 4 H), 3.35 (s, 3 H), 3.34 (s, 3 H), 2.39 (t, J = 1.9 Hz, 2 H), 2.33 (d, J = 2.6 Hz, 2 H), 1.98 (t, J = 2.6 Hz, 1 H), 1.76 (d, J = 6.6 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.0, 130.7, 130.3, 125.9, 83.0, 80.8, 78.2, 73.6, 70.4, 69.7, 59.4, 57.3, 41.8, 22.2, 21.9, 18.1. HRMS: m/z calcd for C₁₈H₂₆O₃: 290.1882; found: 290.1883.
Compound 3d: yield 71%. ¹H NMR (CDCl₃): δ = 6.22 (dd, J = 10.4, 15.0 Hz, 1 H), 6.06 (m, 1 H), 5.74 (m, 1 H), 5.60 (m, 1 H), 4.31 (t, J = 1.7 Hz, 2 H), 4.25 (s, 2 H), 4.18 (t, J = 1.7 Hz, 2 H), 4.06 (d, J = 6.4 Hz, 2 H), 2.45 (m, 1 H), 1.75 (d, J = 6.7 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.3, 130.8, 130.6, 125.7, 83.3, 81.4, 79.0, 75.1, 70.2, 57.1, 56.9, 56.5, 18.2. HRMS: m/z calcd for C₁₃H₁₆O₂: 204.1150; found: 204.1155.
Compound 4d: yield 83%. ¹H NMR (CDCl₃): δ = 6.23 (dd, J = 10.5, 14.9 Hz, 1 H), 6.06 (m, 1 H), 5.74 (m, 1 H), 5.60 (m, 1 H), 4.28 (t, J = 1.7 Hz, 2 H), 4.22-4.18 (m, 2 H), 4.17 (d, J = 1.7 Hz, 2 H), 4.06 (d, J = 6.4 Hz, 2 H), 1.86 (m, 3 H), 1.76 (d, J = 6.4 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.2, 130.8, 130.5, 125.7, 83.2, 82.8, 81.8, 74.4, 70.1, 57.2, 57.1, 56.6, 18.2, 3.6. HRMS: m/z calcd for C₁₄H₁₈O₂: 218.1307; found: 218.1309.
Compound 5d: yield 77%. ¹H NMR (CDCl₃): δ = 6.23 (dd, J = 10.5, 15.0 Hz, 1 H), 6.07 (dd, J = 10.5, 15.0 Hz, 1 H), 5.73 (m, 1 H), 5.61 (m, 1 H), 4.29 (s, 2 H), 4.23 (t, J = 1.7 Hz, 2 H), 4.18 (s, 2 H), 4.07 (d, J = 6.4 Hz, 2 H), 2.23 (t, J = 6.8 Hz, 2 H), 1.76 (d, J = 6.6 Hz, 3 H), 1.47 (m, 2 H), 1.42 (m, 2 H), 0.91 (t, J = 7.2 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.4, 130.8, 130.7, 125.8, 82.9, 81.9, 75.1, 70.2, 57.4, 57.2, 56.7, 31.8, 30.8, 22.1, 18.6, 18.3, 13.8. HRMS: m/z calcd for C₁₇H₂₄O₂: 260.1776; found: 260.1776.
Compound 6d: yield 66%. ¹H NMR (CDCl₃): δ = 7.47-7.44 (m, 2 H), 7.33-7.30 (m, 3 H), 6.23 (dd, J = 10.4, 15.0 Hz, 1 H), 6.06 (m, 1 H), 5.73 (m, 1 H), 5.61 (m, 1 H), 4.48 (s, 2 H), 4.38 (t, J = 1.7 Hz, 2 H), 4.20 (t, J = 1.7 Hz, 2 H), 4.08 (d, J = 6.5 Hz, 2 H), 1.75 (d, J = 6.8 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 134.2, 131.8, 130.6, 130.5, 128.5, 128.3, 125.6, 122.4, 86.8, 84.2, 83.1, 81.5, 70.1, 57.3, 57.1, 56.9, 18.1. HRMS: m/z calcd for C₁₉H₂₀O₂: 280.1463; found: 280.1469.
Compound 7d: yield 65%. ¹H NMR (CDCl₃): δ = 7.42-7.30 (m, 4 H), 7.30-7.09 (m, 6 H), 6.71 (dd, J = 10.5, 15.6 Hz, 1 H), 6.48 (d, J = 15.6 Hz, 1 H), 5.37 (dd, J = 10.5, 15.2 Hz, 1 H), 5.79 (dt, J = 6.3, 15.2 Hz, 1 H), 4.42 (s, 2 H), 4.31 (t, J = 1.7 Hz, 2 H), 4.16 (t, J = 1.7 Hz, 2 H), 4.09 (d, J = 6.3 Hz, 2 H). ¹³C NMR (CDCl₃): δ = 137.2, 134.0, 133.3, 131.9, 129.1, 128.8, 128.7, 128.5, 128.2, 127.8, 126.6, 122.6, 87.0, 84.3, 83.1, 81.9, 70.1, 57.5, 57.4, 57.0. HRMS: m/z calcd for C₂₄H₂₂O₂: 342.1620; found: 342.1613.
Compound 8d: yield 70%. ¹H NMR (CDCl₃): δ = 7.57 (d, J = 8.2 Hz, 2 H), 7.27-7.25 (m, 2 H), 7.17-7.09 (m, 3 H), 7.13 (d, J = 8.2 Hz, 2 H), 5.99 (dd, J = 10.4, 15.0 Hz, 1 H), 5.84 (m, 1 H), 5.54 (m, 1 H), 5.25 (m, 1 H), 4.08 (s, 2 H), 3.96 (s, 2 H), 3.90 (s, 2 H), 3.66 (d, J = 6.9 Hz, 2 H), 2.22 (s, 3 H), 1.57 (d, J = 6.6 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 143.7, 136.3, 135.7, 131.9, 131.2, 130.5, 129.7, 128.9, 128.6, 128.0, 123.6, 122.6, 87.0, 84.2, 81.0, 80.0, 57.3, 56.7, 48.7, 36.2, 21.7, 18.2. HRMS: m/z calcd for C₂₆H₂₇O₃N₁S₁: 433.1712; found: 433.1715.
Compound 1: yield 23%. ¹H NMR (CDCl₃): δ = 6.07 (dt, J = 3.3, 8.8 Hz, 1 H), 5.80 (s, 1 H), 5.48 (dt, J = 3.0, 8.8 Hz, 1 H), 4.49 (dd, J = 7.0, 11.4 Hz, 1 H), 4.20 (dd, J = 7.1, 9.0 Hz, 1 H), 3.83 (d, J = 8.3 Hz, 1 H), 3.67 (d, J = 8.3 Hz, 1 H), 2.85 (m, 1 H), 2.28 (m, 1 H), 2.62 (d, J = 8.3 Hz, 2 H), 1.85 (m, 2 H), 1.75 (m, 2 H), 1.21 (d, J = 7.4 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 212.6, 189.8, 135.1, 130.2, 125.2, 69.7, 69.5, 68.5, 58.0, 44.9, 43.5, 31.0, 29.6, 25.2, 16.6. IR: 1694 (C=O) cm^-1. HRMS: m/z calcd for C₁₅H₁₈O₂: 230.1307; found: 230.1301.
Compound 2: yield 55%. ¹H NMR (CDCl₃): δ = 5.98 (dt, J = 3.2, 8.8 Hz, 1 H), 5.74 (s, 1 H), 5.43 (dt, J = 2.9, 8.8 Hz, 1 H), 4.39 (dd, J = 7.0, 11.3 Hz, 1 H), 4.11 (dd, J = 7.2, 8.8 Hz, 1 H), 3.76 (d, J = 8.5 Hz, 1 H), 3.57 (d, J = 8.4 Hz, 1 H), 3.39 (d, J = 2.3 Hz, 2 H), 3.33 (s, 3 H), 3.17 (s, 3 H), 2.85 (dd, J = 9.0, 16.0, 2 H), 2.72 (m, 1 H), 2.60 (dd, J = 1.8, 15.6 Hz, 1 H), 2.37 (d, J = 15.6 Hz, 1 H), 2.16 (m, 1 H), 1.86 (d, J = 14.9 Hz, 1 H), 1.56 (d, J = 14.9 Hz, 1 H), 1.15 (d, J = 7.4 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 212.2, 188.4, 134.4, 130.6, 126.7, 76.1, 75.5, 69.7, 69.6, 69.5, 59.2, 59.0, 56.6, 48.5, 44.5, 44.4, 37.2, 35.2, 16.6. IR: 1698 (C=O) cm^-1. HRMS: m/z calcd for C₁₉H₂₆O₄: 318.1831; found: 318.1830.
Compound 3: yield 19%. ¹H NMR (CDCl₃): δ = 6.11 (dt, J = 3.3, 8.8 Hz, 1 H), 5.95 (s, 1 H), 5.50 (dt, J = 3.0, 8.8 Hz, 1 H), 4.68 (dd, J = 2.0, 16.4 Hz, 1 H), 4.52 (d, J = 16.4 Hz, 1 H), 4.48 (dd, J = 7.2, 11.4 Hz, 1 H), 4.19 (dd, J = 7.2, 8.8 Hz, 1 H), 4.04 (d, J = 8.8 Hz, 1 H), 3.77 (d, J = 8.4 Hz, 1 H), 3.73 (d, J = 8.4 Hz, 1 H), 3.71 (d, J = 8.8 Hz, 1 H), 2.89 (m, 1 H), 2.52 (m, 1 H), 1.33 (d, J = 7.4 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 210.7, 183.1, 135.0, 130.1, 124.8, 74.1, 68.9, 68.5, 67.3, 66.9, 58.4, 45.3, 42.1, 15.9. IR: 1706 (C=O) cm^-1. HRMS: m/z calcd for C₁₄H₁₆O₃: 232.1099; found: 232.1098.
Compound 4: yield 64%. ¹H NMR (CDCl₃): δ = 6.08 (dt, J = 3.2, 8.8 Hz, 1 H), 5.47 (dt, J = 3.0, 8.8 Hz, 1 H), 4.62 (d, J = 15.8 Hz, 1 H), 4.51 (t, J = 11.4 Hz, 1 H), 4.50 (d, J = 11.6 Hz, 1 H), 4.20 (dd, J = 7.1, 8.8 Hz, 1 H), 4.03 (d, J = 8.5 Hz, 1 H), 3.76 (d, J = 8.3 Hz, 1 H), 3.66 (d, J = 8.6 Hz, 2 H), 2.90 (m, 1 H), 2.49 (m, 1 H), 1.70 (s, 3 H), 1.32 (d, J = 7.4 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 210.8, 175.5, 135.4, 133.3, 129.9, 74.3, 69.1, 68.8, 66.8, 66.4, 56.4, 45.7, 42.3, 16.0, 9.4. IR: 1707 (C=O) cm^-1. HRMS: m/z calcd for C₁₅H₁₈O₃: 246.1256; found: 246.1258.
Compound 5: yield 57%. ¹H NMR (CDCl₃): δ = 6.08 (dt, J = 3.2, 8.8 Hz, 1 H), 5.46 (dt, J = 3.0, 8.8 Hz, 1 H), 4.62 (d, J = 15.9 Hz, 1 H), 4.53 (t, J = 3.5 Hz, 1 H), 4.49 (d, J = 7.3 Hz, 1 H), 4.20 (dd, J = 7.1, 8.8 Hz, 1 H), 4.02 (d, J = 8.8 Hz, 1 H), 3.77 (d, J = 8.3 Hz, 1 H), 3.65 (d, J = 8.3 Hz, 2 H), 2.88 (m, 1 H), 2.48 (m, 1 H), 2.25 (m, 1 H), 2.03 (m, 1 H), 1.36 (m, 2 H), 1.32 (d, J = 7.3 Hz, 3 H), 1.27 (m, 2 H), 0.89 (t, J = 3.5 Hz, 3 H). ¹³C NMR (CDCl₃): δ = 210.7, 175.4, 137.7, 135.3, 130.3, 74.4, 69.2, 68.8, 67.0, 66.5, 56.5, 45.7, 42.4, 30.1, 24.2, 22.6, 16.2, 14.0. IR: 1708 (C=O) cm^-1. HRMS: m/z calcd for C₁₈H₂₄O₃: 288.1725; found: 288.1723.
Compound 6. yield 73%. ¹H NMR (CDCl₃): δ = 7.50-7.47 (m, 2 H), 7.40-7.34 (m, 3 H), 6.11 (dt, J = 3.3, 8.8 Hz, 1 H), 5.51 (dt, J = 3.0, 8.8 Hz, 1 H), 4.97 (d, J = 16.7 Hz, 1 H), 4.61 (t, J = 3.5 Hz, 1 H), 4.56 (d, J = 7.4 Hz, 1 H), 4.25 (dd, J = 7.1, 9.1 Hz, 1 H), 4.09 (d, J = 8.8 Hz, 1 H), 3.82 (d, J = 4.0 Hz, 2 H), 3.68 (d, J = 8.8 Hz, 1 H), 2.96 (m, 1 H), 2.59 (m, 1 H), 1.42 (d, J = 7.4 Hz, 1 H). ¹³C NMR (CDCl₃): δ = 208.4, 176.6, 135.1, 134.8, 130.4, 130.2, 128.8, 128.5, 128.2, 73.7, 69.1, 68.5, 68.1, 67.8, 56.2, 45.5, 42.6, 16.0. IR: 1706 (C=O) cm^-1. HRMS: m/z calcd for C₂₀H₂₀O₃: 308.1412; found: 308.1413.
Compound 7: yeld 52%. ¹H NMR (CDCl₃): δ = 7.46-7.34 (m, 4 H), 7.33-7.25 (m, 6 H), 6.63 (d, J = 16.2 Hz, 1 H), 6.17 (dd, J = 6.7, 16.2 Hz, 1 H), 4.98-4.85 (m, 2 H), 4.85 (d, J = 7.4 Hz, 1 H), 4.37 (dd, J = 7.2, 9.1 Hz, 1 H), 4.09 (d, J = 9.0 Hz, 1 H), 4.06 (d, J = 8.8 Hz, 2 H), 3.92 (d, J = 8.8 Hz, 1 H), 3.09 (m, 1 H), 2.68 (m, 1 H). ¹³C NMR (CDCl₃): δ = 207.9, 176.5, 135.2, 135.0, 130.3, 129.0, 128.8, 128.6, 128.5, 128.4, 128.2, 128.0, 127.8, 73.3, 69.0, 68.5, 67.9, 67.8, 56.1, 45.5, 42.4. IR: 1705 (C=O) cm^-1. HRMS: m/z calcd for C₂₅H₂₂O₃: 370.1569; found: 370.1564.
Compound 8: yield 59%, ¹H NMR (CDCl₃): δ = 7.70 (d, J = 8.2 Hz, 2 H), 7.30 (d, J = 8.2 Hz, 2 H), 7.26-7.23 (m, 3 H), 7.07-7.01 (m, 2 H), 5.89 (dt, J = 3.2, 8.9 Hz, 1 H), 5.33 (dt, J = 2.9, 8.9 Hz, 1 H), 4.83 (d, J = 16.8 Hz, 1 H), 4.43 (d, J = 16.8 Hz, 1 H), 4.01 (dd, J = 7.1, 8.9 Hz, 1 H), 3.98 (d, J = 8.9 Hz, 1 H), 3.61 (s, 2 H), 3.41 (d, J = 10.6 Hz, 1 H), 3.14 (d, J = 10.6 Hz, 1 H), 2.73 (m, 1 H), 2.44 (s, 3 H), 2.40 (m, 1 H). ¹³C NMR (CDCl₃): δ = 207.2, 176.3, 143.3, 135.0, 134.9, 134.5, 130.6, 130.0, 129.6, 128.9, 128.5, 128.2, 127.6, 73.7, 68.1, 67.1, 65.2, 56.8, 49.3, 43.6, 41.9, 21.6, 16.0. IR: 1706 (C=O) cm^-1. HRMS: m/z calcd for C₂₇H₂₇O₄N₁S₁: 461.1661; found: 461.1664.

Compound 3: C₁₄H₁₆O₃, M = 232.27, monoclinic, space group P2 (1)/c, a = 8.223 (2) Å, b = 8.552 (3) Å, c = 16.543 (3) Å, β = 91.633 (19), V = 1163.0(5) Å³, Z = 4, D _c = 1.327 mg m^-3, µ(MoK_α) = 0.092 mm^-1, F(000) = 496. No. of data collected: 2769, no. of unique data: 949, R = 0.0641, R _w = 0.1749. A single crystal was placed on an Enraf-Nonius CCD single crystal X-ray diffractometer. The structures were solved by direct methods (SHELXS-97) and refined against all F ² data (SHELXS-97). All non-hydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms were treated as idealized contributions. Data collected at 293 (2) K with MoK_α radiation: λ(K_α) = 0.7107 Å), R(F) = Σ| |F _o| - |F _c| |/Σ|F _o| with F _o > 2.0σ (I), R _w = [Σ [w(F _o ² - F _c ²)²]/Σ[w(F _o)²]²]^1/2 with F _o > 2.0σ (I). CCDC reference number 272770.

<A NAME="RU09505ST-9">9</A> Sugawara S. Uemura K. Tsukada N. Inoue Y. J. Mol. Catal. A: Chem. 2003, 195: 55