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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;
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Publication History

Received 21 November 2003
Publication Date:
29 January 2004 (online)

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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

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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.