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

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Synlett 2005(12): 1889-1892
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;

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Publication History

Received 1 April 2005
Publication Date:
07 July 2005 (online)

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

References

For recent reviews, see:
1a Carreno MC. Urbano A. Synlett 2005, 1

Crossref Google Scholar
1b Rodríguez Rivero M. Adrio J. Carretero JC. Synlett 2005, 26

Crossref Google Scholar
1c France S. Weatherwax A. Taggi AE. Lectka T. Acc. Chem. Res. 2004, 37: 592

Crossref Google Scholar
1d Harvey RG. Curr. Org. Chem. 2004, 8: 303

Crossref Google Scholar
1e Denissova I. Barriault L. Tetrahedron 2003, 59: 10105

Crossref Google Scholar
For recent reviews, see:
2a Bolm C. Legros J. Le Paih J. Zani L. Chem. Rev. 2004, 104: 6217

Crossref PubMed Google Scholar
2b Montgomery J. Angew. Chem. Int. Ed. 2004, 43: 3890

Crossref PubMed Google Scholar
2c Zeni G. Larock RC. Chem. Rev. 2004, 104: 2285

Crossref PubMed Google Scholar
2d Nakamura I. Yamamoto Y. Chem. Rev. 2004, 104: 2127

Crossref PubMed Google Scholar
2e Varela JA. Saa C. Chem. Rev. 2003, 103: 3787

Crossref PubMed Google Scholar
3a Ajamian A. Gleason L. Angew. Chem. Int. Ed. 2004, 43: 3754

Crossref PubMed Google Scholar
3b Lee JM. Na Y. Han H. Chang S. Chem. Soc. Rev. 2004, 33: 302

Crossref PubMed Google Scholar
3c Fogg DE. dos Santos EN. Coord. Chem. Rev. 2004, 248: 2365

Crossref PubMed Google Scholar
3d Wasilke J.-C. Obrey SJ. Baker RT. Bazan GC. Chem. Rev. 2005, 105: in press

Crossref PubMed Google Scholar
3e Ramon DJ. Yus M. Angew. Chem. Int. Ed. 2005, 44: 1602

Crossref PubMed Google Scholar
4 Wender PA. Gamber G. Hubbard RD. Pham SM. Zhang L. J. Am. Chem. Soc. 2005, in press; and references therein

Google Scholar
5 Kim DH. Chung YK. Chem. Commun. 2005, 1634

Crossref Google Scholar
6a Son SU. Park KH. Lee SJ. Kim BM. Chung YK. Synlett 2003, 1101

Crossref Google Scholar
6b Kim DH. Son SU. Chung YK. Lee S.-G. Chem. Commun. 2002, 56

Crossref Google Scholar
6c Son SU. Yoon YA. Choi DS. Park JK. Kim BM. Org. Lett. 2001, 3: 1065

Crossref Google Scholar
6d Son SU. Chung YK. Lee SG. J. Org. Chem. 2000, 65: 6142

Crossref Google Scholar
6e Son SU. Choi DS. Chung YK. Org. Lett. 2000, 2: 2097

Crossref Google Scholar
6f Hong SH. Choi DS. Chung YK. Lee S. Chem. Commun. 1999, 2099

Crossref Google Scholar
9 Sugawara S. Uemura K. Tsukada N. Inoue Y. J. Mol. Catal. A: Chem. 2003, 195: 55

Crossref Google Scholar

7

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.

8

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.