PDF herunterladen
Synlett 2004(4): 717-719  
DOI: 10.1055/s-2004-815441
LETTER
© Georg Thieme Verlag Stuttgart · New York

New Synthesis of Substituted Cyclopentanes via Reactions of γ-Chloro-carbanions with Electron-deficient Alkenes

Mieczysław Mąkosza*, Marek Judka
Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44, 01-224 Warszawa 42, POB 58, Poland
Fax: +48(22)6326681; e-Mail: icho-s@icho.edu.pl;
Weitere Informationen

Publikationsverlauf

Received 21 November 2003
Publikationsdatum:
29. Januar 2004 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Carbanions of 3-chloropropyl pentachlorophenylsulfone, although they undergo fast cyclization to the corresponding cyclopropyl sulfone, can be trapped with electrondeficient alkenes to produce carbanionic adducts that enter intramolecular substitution to form substituted cyclopentanes.

Key words

carbanions - cyclization - cyclopentane - Michael acceptors - sulfone

    References

  • 1a Gronert S. Azizian K. Friedman MA. J. Am. Chem. Soc.  1998,  120:  3220 
    CrossrefGoogle Scholar
  • 1b Habusha U. Rozental E. Hoz S. J. Am. Chem. Soc.  2002,  124:  15006 
    CrossrefGoogle Scholar
  • 2a McCoy L. J. Am. Chem. Soc.  1960,  82:  6416 
    CrossrefGoogle Scholar
  • 2b Wendish D. In Houben-Weyl, Methoden der organischen Chemie   Vol. IV 3:  , Thieme; Stuttgart: 1971.  p.89 
    CrossrefGoogle Scholar
  • 2c Fleming FF. Shook BC. Tetrahedron  2002,  58:  1 
    CrossrefGoogle Scholar
  • 3 Zwanenburg B. De Kimpe N. In Houben-Weyl, Methoden der organischen Chemie   Vol. E17a:  Thieme; Stuttgart: 1997.  p.45 
    Google Scholar
  • 4 Mann J. Comprehensive Organic Synthesis   Vol. 3:  Trost B. Pergamon; Oxford: 1991.  p.839 
    Google Scholar
  • 5a Paquette LA. Org. React.  1971,  25:  1 
    Google Scholar
  • 5b Clough JM. Comprehensive Organic Synthesis   Vol. 3:  Trost B. Pergamon; Oxford: 1991.  p.861 
    Google Scholar
  • 6a Mkosza M. Przyborowski J. Klajn R. Kwast A. Synlett  2000,  1773 
    Google Scholar
  • 6b Mkosza M. Judka M. Chem.-Eur. J.  2002,  8:  4234 
    Google Scholar
  • 7a Collins SPW. Djuric W. Chem. Rev.  1993,  93:  1533 
    Google Scholar
  • 7b Mathew J. Recent Progress in the Chemical Synthesis of Antibiotics, Lucas G.   Vol. II:  Springer Verlag; Heidelberg: 1993.  p.435 
    Google Scholar
  • 7c Mikolajczyk M. Mikina M. Jankowska A. J. Org. Chem.  2000,  65:  5127 
    Google Scholar
  • 7d Ghosh S. Patra D. Pure Appl. Chem.  1996,  68:  597 
    Google Scholar
  • 8 Hanselaer R. Samson M. Vandewalle M. Tetrahedron  1978,  34:  2393 
    Google Scholar
  • 9a Hudlicky T. Price JD. Chem. Rev.  1989,  89:  1467 
    Google Scholar
  • 9b Thebtaranonth C. Thebtaranonth Y. Tetrahedron  1990,  46:  1385 
    Google Scholar
  • 9c Survey of cyclopentane ring formation, see: Larock RL. Comprehensive Organic Transformations   2nd ed.:  Wiley-VCH; New York: 1999.  p.168-174  
    Google Scholar
  • 9d Du Y. Lu X. Zhang C. Angew. Chem. Int. Ed.  2003,  42:  1035 
    Google Scholar
  • 9e Huart C. Ghosez L. Angew. Chem., Int. Ed. Engl.  1997,  36:  634 
    Google Scholar
  • 10 Silva LF. Tetrahedron  2002,  58:  9137 
    CrossrefGoogle Scholar
11

Typical Procedure. All reactions were performed in oven-dried glassware under argon. THF was freshly distilled from potassium-benzophenone. To a solution of 1 (117 mg, 0.3 mmol) in THF (5 mL) at -70 °C LDA (0.22 mL of 1.8 M solution, 0.4 mmol) was added in one portion. After 1-2 sec Michael acceptor dissolved in THF was added: 0.45 mmol in 0.5 mL of THF for the synthesis of 4, 7, 8, 9, 10; 0.6 mmol for 6, and 3 mmol for 5. The mixture was stirred for 5 min, warmed to r.t., quenched with aq NH4Cl, extracted and purified by column and preparative TLC chromatography (hexane/EtOAc as eluent).
Compound 1: mp 124 °C; 1H NMR (200 MHz, CDCl3): δ = 2.31-2.46 (m, 2 H), 3.67-3.78 (m, 4 H). 13C NMR (50 MHz, CDCl3): δ = 25.93, 43.12, 53.77, 134.51, 135.67, 135.97, 139.83.
Compound 2: mp 169 °C; 1H NMR (400 MHz, CDCl3): δ = 1.12-1.16 (m, 2 H), 1.50-1.55 (m, 2 H), 3.20 [tt, 3 J(H,H) = 4.77, 7.88 Hz, 1 H]. 13C NMR (100 MHz, CDCl3): δ = 6.06, 32.69, 133.20, 134.87, 137.45, 138.47.
Compound 3: cis-isomer, mp 125 °C; 1H NMR (400 MHz, CDCl3): δ = 1.42 (s, 9 H), 2.13-2.26 (m, 3 H), 2.90-3.08 (m, 2 H), 4.59 [dd, 3 J(H,H) = 6.97, 7.43 Hz, 1 H], 4.75-4.80 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 26.53, 27.81, 28.28, 48.83, 66.23, 75.09, 82.76, 132.48, 133.21, 136.81, 168.86.
Compound 3: trans-isomer, mp 120 °C. 1H NMR (400 MHz, CDCl3): δ = 1.42 (s, 9 H), 2.20-2.31 (m, 1 H), 2.33-2.41 (m, 2 H), 2.76-2.83 (m, 1 H), 3.12-3.21 (m, 1 H), 4.27-4.34 (m, 1 H), 4.62 [t, 3 J(H,H) = 6.87 Hz, 1 H], 4.73 [dt, 3 J(H,H) = 2.20, 8.72 Hz, 1 H]. 13C NMR (100 MHz, CDCl3): δ = 26.64, 27.82, 28.59, 49.27, 67.58, 74.68, 82.78, 132.77, 133.28, 136.65, 169.19. Anal. calcd (%) for C16H17Cl5O4S (482.63): C, 39.82; H, 3.55; Cl, 36.73; S, 6.64. Found: C, 39.93; H, 3.63; Cl, 36.82; S, 6.60.
Compound 4: cis-isomer, mp 156 °C; 1H NMR (200 MHz, CDCl3): δ = 2.21-2.33 (m, 2 H), 2.78-2.83 (m, 2 H), 3.31 [t, 3 J(H,H) = 10.01 Hz, 1 H], 4.26-4.44 (m, 1 H), 4.72-4.82 (m, 1 H), 5.57-5.65 (m, 1 H), 7.56-7.94 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 25.02, 28.28, 65.95, 67.85, 75.30, 128.23, 129.35, 129.50,134.17, 134.52, 135.43, 135.84, 139.21.
Compound 4: trans-isomer, oil. 1H NMR (200 MHz, CDCl3): δ = 2.17-2.33 (m, 2 H), 2.89 [dt, 3 J(H,H) = 6.60, 14.43 Hz, 1 H], 3.03-3.20 (m, 2 H), 4.26-4.41 (m, 1 H), 4.72-4.84 (m, 1 H), 5.47-5.54 (m, 1 H), 7.54-7.93 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 25.57, 27.74, 66.91, 68.88, 75.46, 128.42, 129.46, 129,82, 132.96, 133.98, 134.57, 135.18, 138.78.
Comound 5: cis-isomer, mp 197 °C; 1H NMR (400 MHz, CDCl3): δ = 1.98 (s, 3 H), 2.17-2.38 (m, 2 H), 2.64 [dd, 3 J(H,H) = 2.39, 15.96 Hz, 1 H], 2.94 [dd, 3 J(H,H) = 9.36, 15.96 Hz, 1 H], 3.17-3.25 (m, 1 H), 3.73 (s, 3 H), 4.64 [dt, 3 J(H,H) = 2.38, 8.62 Hz, 1 H]. 13C NMR (100 MHz, CDCl3): δ = 26.91, 29.61, 34.58, 53.11, 54.36, 64.93, 73.21 133.67, 133.75, 138.16, 175.53.
Compound 5: trans-isomer, mp 148 °C; 1H NMR (400 MHz, CDCl3): δ = 2.01 (s, 3 H), 2.15-2.22 (m, 2 H), 2.60 [dd, 3 J(H,H) = 4.22, 15.77 Hz, 1 H], 2.92 [dd, 3 J(H,H) = 7.7, 15.59 Hz, 1 H], 3.09-3.16 (m, 1 H), 3.73 (s, 3 H), 4.19-4.25 (m, 1 H), 4.64-4.69 (m, 1 H). 13C NMR (100 MHz, CDCl3): δ = 28.01, 29.54, 34.22, 53.03, 54.36, 64.72, 73.94, 133.65, 133.77, 138.16, 138.58, 175.65.
Compound 6: mp 167 °C; 1H NMR (200 MHz, CDCl3): δ = 1.18 [t, 3 J(H,H) = 7.16 Hz, 3 H], 2.00-2.14 (m, 1 H), 2.38-2.60 (m, 1 H), 3.60 [dd, 3 J(H,H) = 6.00, 11.68 Hz, 1 H], 4.14 [dq, 3 J(H,H) = 2.56, 7.14 Hz, 2 H], 4.25-4.57 (m, 2 H), 4.87-4.96 (m, 2 H), 7.20-7.37 (m, 5 H). 13C NMR (50 MHz, CDCl3): δ = 13.89, 26.05, 44.83, 53.03, 61.62, 72.27, 128.19, 128.98, 130.38, 133.48, 134.47, 135.41, 137.77, 169.33.
Compound 7: mp 232 °C; 1H NMR (400 MHz, CDCl3): δ = 1.90-2.07 (m, 1 H), 2.44-2.55 (m, 1 H), 3.65-3.74 (m, 1 H), 4.41-4.47 (m, 2 H), 4.86 [t, 3 J(H,H) = 7.89 Hz, 1 H], 5.46 [d, 3 J(H,H) = 5.32 Hz, 1 H], 7.23-7.61 (m, 10 H). 13C NMR (100 MHz, CDCl3): δ = 26.09, 45.26, 56.95, 71.99, 76.27, 127.55, 128.16, 128.27, 128.69, 132.58, 133.25, 133.78, 134.70, 136.20, 136.79, 196.14.
Compound 9: trans-isomer, mp 234 °C; 1H NMR (400 MHz, CDCl3): δ = 2.67-2.88 (m, 3 H), 2.92-2.98 (m, 1 H) 4.72 [d, 3 J(H,H) = 9.72 Hz, 1 H], 4.76-4.86 (m, 1 H), 7.23-7.28 (m, 3 H), 7.33-7.38 (m, 1 H). 13C NMR (50 MHz, CDCl3): δ = 23.62, 38.26, 42.20, 50.90, 64.25, 112.81, 113.18, 127.28, 128.11, 128.59, 130.03.61, 130.61, 132.91, 133.76, 135.06, 135.12, 139.48.
Compound 10: trans-isomer, mp 216 °C; 1H NMR (500 MHz, CDCl3): δ = 1.92 [dddd, 3 J(H,H) = 3.40, 6.80, 9.15 Hz, 2 J(H,H) = 15.50 Hz, 1 H], 2.60 [dddd, 3 J(H,H) = 4.95, 5.80, 8.80 Hz, 2 J(H,H) = 15.50 Hz, 1 H], 3.61 [ddd, 3 J(H,H) = 6.80, 4.95 Hz, 2 J(H,H) = 11.50 Hz, 1 H], 3.82 [ddd, 3 J(H,H) = 5.85, 9.10 Hz, 2 J(H,H) = 11.50 Hz, 1 H], 4.26 [ddd, 3 J(H,H) = 12.00, 8.80, 3.40 Hz, 1 H], 4.42 [d, 3 J(H,H) = 12.00 Hz, 1 H], 6.57 [dd, 3 J(H,H) = 1.90, 3.40 Hz, 1 H], 6.83 [d, 3 J(H,H) = 3.35 Hz, 1 H], 7.65 [d, 3 J(H,H) = 1.55 Hz, 1 H]. 13C NMR (100 MHz, CDCl3): δ = 28.21, 40.87, 42.65, 45.02, 56.77, 110.04, 111.03, 111.56, 114.71, 123.84, 132.18, 133.96, 136.57, 139.98, 140.18, 143.53, 145.29.
Compound 10: cis-isomer, mp 158 °C; 1H NMR (400 MHz, CDCl3): δ = 2.60-2.89 (m, 4 H), 4.17 [d, 3 J(H,H) = 10.08 Hz, 1 H], 4.87-4.95 (m, 1 H), 6.19 [dd, 3 J(H,H) = 1.47, 3.30 Hz, 1 H], 6.29 [d, 3 J(H,H) = 3.29 Hz, 1 H], 7.24 [d, 3 J(H,H) = 1.28 Hz, 1 H]. 13C NMR (100 MHz, CDCl3): δ = 23.03, 37.23, 41.77, 50.53, 62.59, 110.68, 110.86, 112.73, 113.34, 133.55, 133.78, 135.04, 139.56, 144.15, 144.28.