Dianionic Cycloaddition of Decatetraenes with RCOX Forming Nine-Membered Carbocycles

Lian  Leng; Chanjuan  Xi; Yongling  Shi; Baohua  Guo

doi:10.1055/s-2003-36807

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Synlett 2003(2): 0183-0186
DOI: 10.1055/s-2003-36807

LETTER

Dianionic Cycloaddition of Decatetraenes with RCOX Forming Nine-Membered Carbocycles

Lian Leng^a, Chanjuan Xi*^a, Yongling Shi^a, Baohua Guo^b
^a Key Laboratory for Bioorganic Phosphorus Chemistry of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084, China
Fax: +86(10)62566383; e-Mail: cjxi@tsinghua.edu.cn;
^b Institute of Polymer Science and Engineering, Department of Chemical and Engineering, Tsinghua University, Beijing, 100084, China

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Publication History

Received 20 November 2002
Publication Date:
22 January 2003 (online)

Abstract
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Abstract

2,9-Dilithio-1,4,6,9-decatetraenes, generated from the corresponding dibromo-decatetraenes, were reacted with acyl halides or carboxylic esters to give nine-membered carbocycles. The decatetraene precursors were readily prepared from zirconacyclopentadienes and 2,3-dibromopropene in the presence of a catalytic amount of CuCl.

Key words

cycloadditions - zirconacyclopentadiene - dibromodecatetraene - nine-membered carbocycles - acyl chloride

References

1a Devon TK. Scott AI. Handbook of Naturally Occurring Compounds Vol. II: Academic Press; New York and London: 1972.

Crossref Search in Google Scholar
1b Faulkner DJ. Nat. Prod. Rep. 1984, 125: 551

Crossref Search in Google Scholar
1c Faulkner DJ. Nat. Prod. Rep. 1989, 5: 613

Crossref Search in Google Scholar
2 Illuminati G. Mandolini L. Acc. Chem. Res. 1981, 14: 95

Crossref Search in Google Scholar
3a Ziegler K. In Houben-Weyl Methoden der Organischen Chemie Vol. 4/2: Müller E., Thieme; Stuttgart: 1955.

Search in Google Scholar
3b Smith MB. Organic Synthesis McGraw-Hill; New York: 1994. p.611
4a Mukaiyama T. Angew. Chem., Int. Ed. Engl. 1979, 18: 707

Search in Google Scholar
4b Mulzer J. Angew. Chem., Int. Ed. Engl. 1991, 30: 1452

Search in Google Scholar
4c Corey EJ. Ulrich P. Fitzpatrick JM. J. Am. Chem. Soc. 1976, 98: 222

Search in Google Scholar
4d Hikota M. Tone H. Horita K. Yonemitsu O. J. Org. Chem. 1990, 55: 7

Search in Google Scholar
For reviews, see:
5a Petasis NA. Patane MA. Tetrahedron 1992, 48: 5757

Search in Google Scholar
5b Sieburth S. Cunard NT. Tetrahedron 1996, 52: 6251

Search in Google Scholar
5c Lautens M. Klute W. Tam W. Chem. Rev. 1996, 96: 49

Search in Google Scholar
5d Frühauf W.-H. Chem. Rev. 1997, 97: 523

Search in Google Scholar
5e Yet L. Chem. Rev. 2000, 100: 2963

Search in Google Scholar
6 Takahashi T. Kotora M. Kasai K. Suzuki N. Nakajima K. Organometallics 1994, 13: 4183

Crossref Search in Google Scholar
7a Watt GW. Drummond FO. J. Am. Chem. Soc. 1970, 92: 826

Crossref Search in Google Scholar
7b Alt H. Rausch MD. J. Am. Chem. Soc. 1974, 96: 5936

Crossref Search in Google Scholar
7c Buchwald SL. Watson BT. Huffman JC. J. Am. Chem. Soc. 1987, 109: 2544

Crossref Search in Google Scholar
7d Negishi E. Cederbaum FE. Takahashi T. Tetrahedron Lett. 1986, 27: 2829

Crossref Search in Google Scholar
7e Takahashi T. Kageyama M. Denisov V. Hara R. Negishi E. Tetrahedron Lett. 1993, 34: 687

Crossref Search in Google Scholar
7f Xi Z. Hara R. Takahashi T. J. Org. Chem. 1995, 60: 4444

Crossref Search in Google Scholar

8

2,9-Dibromo-4,5,6,7-tetraethyl-deca-1,4,6,9-tetraene (2a): ¹H NMR (CDCl₃- SiMe₄): δ = 5.54 (s, 2 H), 5.46 (s, 2 H), 3.21-3.27 (d, J = 16.2 Hz, 2 H), 3.04-3.10 (d, J = 16.2 Hz, 2 H), 2.04-2.31 (m, 8 H), 0.98-1.03 (t, J = 7.2 Hz, 12 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 139.85 (2 C), 133.30 (2 C), 132.20 (2 C), 117.40 (2 C), 44.13 (2 C), 25.09 (2 C), 22.75 (2 C), 13.50 (2 C), 13.32 (2 C). HRMS calcd for C₁₈H₂₈Br₂: 402.0558; found: 402.0551.

9

2,9-Dibromo-4,5,6,7-tetrapropyl-deca-1,4,6,9-tetraene (2b): ¹H NMR (CDCl₃-SiMe₄): δ = 5.52 (s, 2 H), 5.45 (s, 2 H), 3.20-3.26 (d, J = 16.2 Hz, 2 H), 3.02-3.08 (d, J = 16.2 Hz, 2 H), 2.01-2.18 (m, 8 H), 1.26-1.53 (m, 8 H), 0.93-0.95 (t, J = 7.2 Hz, 6 H), 0.88-0.90 (t, J = 7.2 Hz, 6 H); ¹³C NMR (CDCl₃ SiMe₄): δ = 139.83 (2 C), 133.37 (2 C), 130.96 (2 C), 117.33 (2 C), 44.65 (2 C), 34.97 (2 C), 32.06 (2 C), 29.73 (2 C), 22.27 (2 C), 22.01 (2 C), 14.84 (2 C), 14.46 (2 C). HRMS calcd for C₂₄H₃₆Br₂: 458.1184; found: 458.1192.

10

2,9-Dibromo-4,5,6,7-tetraphenyl-deca-1,4,6,9-tetraene (2c): ¹H NMR (CDCl₃-SiMe₄): δ = 6.94-7.12 (m, 20 H), 5.27 (s, 2 H), 5.20 (s, 2 H), 3.95 (s, 2 H); 3.90 (s, 2 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 142.22, 140.57, 140.26, 136.83, 130.47, 130.33, 129.70, 127.74, 127.55, 126.67, 126.52, 118.89 (2 C), 47.46 (2 C). HRMS calcd for C₃₄H₂₈Br₂: 594.0558; found: 594.0563.

11

1,2-Bis-(3-bromo-1-hexyl-but-3-enylidene)-cyclohexane (2d): ¹H NMR (CDCl₃-SiMe₄): δ = 5.57 (s, 2 H), 5.42 (s, 2 H), 3.26-3.31 (d, J = 14.4 Hz, 2 H), 2.85-2.90 (d, J = 15.3 Hz, 2H), 2.70-2.74 (d, J = 11.7 Hz, 2 H), 1.83-2.22 (m, 6 H), 1.28-1.61 (m, 20 H), 0.86-0.88 (t, J = 6.6 Hz, 6 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 139.91(2 C), 133.54 (2 C), 126.51 (2 C), 117.14 (2 C), 44.40 (2 C), 32.80 (2 C), 31.75 (2 C), 29.47 (2 C), 29.42 (2 C), 28.95 (2 C), 28.85 (2 C), 22.67 (2 C), 14.07 (2 C). HRMS calcd for C₂₆H₄₂Br₂: 512.1653; found: 512.1660.

12

4,5,6,7-Tetraethyl-1-methyl-2,9-dimethylene-cyclonona-4,6-dienol (4a): ¹H NMR (CDCl₃-SiMe₄): δ = 5.08-5.14 (d, J = 18 Hz, 2 H), 4.88 (s, 2 H), 3.18-3.23 (d, J = 13.2 Hz, 1 H), 3.04-3.09 (d, J = 14.1 Hz, 1 H), 2.67-2.72 (d, J = 14.1 Hz, 1 H), 2.51-2.55 (d, J = 13.8 Hz, 1 H), 1.86-2.41 (m, 8 H), 1.45 (s, 1 H), 1.26 (s, 3 H), 0.97-1.06 (t, J = 7.2 Hz, 9 H), 0.86-0.91 (t, J = 7.5 Hz, 3 H); ¹³C NMR (CDCl₃-SiMe₄):
δ = 154.74, 154.13, 137.80, 136.18, 135.08, 134.92, 110.87, 110.73, 78.50, 37.47, 37.38, 29.56, 24.44, 23.66, 23.50, 22.82, 13.05,12.86,12.47,12.21. HRMS calcd for C₂₀H₃₂O: 288.2453; found: 288.2461.

13

4,5,6,7-Tetraethyl-2,9-dimethylene-1-phenyl-cyclonona-4,6-dienol (4a′): ¹H NMR (CDCl₃-SiMe₄): δ = 7.18-7.37 (m, 5 H), 5.58 (s, 1 H), 5.39 (s, 1 H), 5.35 (s, 1 H), 5.29 (s, 1 H), 3.36-3.41 (d, J = 13.2 Hz, 2 H), 2.62-2.67 (d, J = 14.1 Hz, 2 H), 1.74-2.55 (m, 9 H), 1.26 (s, 1 H), 0.88-1.04 (t, J = 7.5 Hz, 6 H), 0.80-0.85 (t, J = 7.5 Hz, 3 H), 0.53-0.58 (t, J = 7.2 Hz, 3 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 153.03, 151.93, 145.70, 137.48, 136.32, 134.77, 133.84, 127.68 (2 C), 127.64 (2 C), 127.13, 118.34, 113.04, 84.99, 39.81, 36.79, 24.08, 23.29, 23.10, 22.38, 13.23, 13.01, 12.73, 12.24. HRMS calcd for C₂₅H₃₄O: 350.2610; found: 350.2617.

14

1-Methyl-2,9-dimethylene-4,5,6,7-tetrapropyl-cyclonona-4,6-dienol (4b): ¹H NMR (CDCl₃-SiMe₄): δ = 5.10-5.15 (d, J = 15 Hz, 2 H), 4.86 (s, 2 H), 3.19-3.24 (d, J = 13.8 Hz, 1 H), 3.03-3.08 (d, J = 14.1 Hz, 1 H), 2.63-2.68 (d, J = 13.8 Hz, 1 H), 2.47-2.51 (d, J = 13.8 Hz, 1 H), 1.12-2.19 (m, 20 H), 0.86-0.95 (t, J = 7.2 Hz, 12 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 154.86, 154.02, 138.02, 136.74, 133.58, 133.44, 110.91, 110.67, 78.58, 37.79, 37.49, 33.53, 33.50, 33.32, 31.89, 29.69, 29.64, 22.68, 21.44, 21.40, 21.20, 14.86, 14.77, 14.21, 14.14. HRMS calcd for C₂₄H₄₀O: 344.3079; found: 344.3086.

15

2,9-Dimethylene-1,4,5,6,7-pentapropyl-cyclonona-4,6-dienol (4b′): ¹H NMR (CDCl₃-SiMe₄): δ = 5.21 (s, 1 H), 5.18 (s, 1 H), 5.02 (s, 1 H), 4.85 (s, 1 H), 3.23-3.28 (d, J = 13.8 Hz, 1 H), 2.92-2.97(d, J = 13.8 Hz, 1 H), 2.62-2.67 (d, J = 13.2 Hz, 1 H), 2.45-2.50 (d, J = 13.8 Hz, 1 H), 1.26 (s, 1 H), 1.46-2.31 (m, 27 H), 0.85-1.05 (t, J = 7.2 Hz, 12 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 154.95, 152.63, 137.29, 136.75, 133.92, 133.48, 112.04, 111.45, 81.22, 43.76, 39.27, 36.31, 33.26, 33.05, 31.23, 29.69, 21.52, 21.48, 21.29, 21.11, 16.94, 14.86, 14.69, 14.46, 14.20, 14.10. HRMS calcd for C₂₆H₄₄O: 372.3392; found: 372.3401.

16

2,9-Dimethylene-1,4,5,6,7-pentaphenyl-cyclonona-4,6-dienol (4c): ¹H NMR (CDCl₃-SiMe₄): δ = 6.70-7.23 (m, 25 H), 5.34 (s, 1 H), 5.10-5.14 (d, J = 13.8 Hz, 1 H), 4.64 (s, 1 H), 4.49-4.54 (d, J = 14.1 Hz, 1 H), 3.78-3.83 (d, J = 14.1Hz, 2 H), 3.51-3.556 (d, J = 14.1 Hz, 2 H), 1.98 (s, 1 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 149.31, 144.83, 142.20, 140.69, 140.17, 139.85, 139.50, 139.05, 138.85, 130.94, 130.57, 130.48, 130.37, 128.00, 127.84, 127.74, 127.40, 127.21, 127.07, 127.03, 126.523, 126.36, 125.77, 121.00, 115.05, 85.80, 41.19, 40.05. HRMS calcd for C₄₁H₃₄O: 542.2610; found: 542.2601.

17

5,11-Dihexyl-7,9-dimethylene-8-phenyl-2,3,4,6,7,8,910-octahydro-1H-benzocycononen-8-ol (4d): ¹H NMR (CDCl₃-SiMe₄): δ = 7.20-7.38 (m, 5 H), 5.38-5.50 (d, J = 34.8 Hz, 2 H), 5.26-5.37 (d, J = 32.4 Hz, 2 H), 3.30-3.45 (m, 4 H), 1.26-2.71 (m, 28 H), 0.88-1.09 (m, 6 H); ¹³C NMR (CDCl₃ SiMe₄): δ = 152.2, 152.31, 146.18, 136.81, 136.74, 129.84, 129.58, 127.69, 127.41, 126.94, 117.71, 113.12, 84.88, 39.91, 37.14, 31.97, 31.86, 31.80, 31.56, 31.42, 29.84, 29.67, 29.53, 29.10, 28.80, 28.60, 28.43, 22.66, 14.07 (2 C). HRMS calcd for C₃₃H₄₈O 460.3705; found 460.3710.

18

4,5,6,7-Tetraethyl-2-methylene-deca-4,6,9-trienoic acid methylester (4f): ¹H NMR (CDCl₃-SiMe₄): δ = 6.20 (s, 2 H), 5.40-5.88 (m, 2 H), 4.95-4.98 (m, 1 H), 3.76 (s, 3 H), 3.06-3.11 (d, J = 13.8 Hz, 2 H), 2.93-2.98 (d, J = 13.8 Hz, 2 H), 1.96-2.21 (m, 8 H), 0.87-1.03 (t, J = 7.2 Hz, 12 H); ¹³C NMR (CDCl₃-SiMe₄): δ = 168.26, 139.63, 139.21, 137.62, 136.03, 134.38, 131.81, 125.27, 115.46, 51.82, 37.29, 33.63, 29.72, 24.56, 24.44, 23.08, 22.70, 13.61, 13.44, 13.21, 13.12. HRMS calcd for C₂₀H₃₂O₂: 304.2402; found: 304.2413.