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

Mieczysław Mąkosza; Marek Judka

doi:10.1055/s-2004-815441

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Synlett 2004(4): 717-719
DOI: 10.1055/s-2004-815441

LETTER

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)

Abstract
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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

References

1a Gronert S. Azizian K. Friedman MA. J. Am. Chem. Soc. 1998, 120: 3220

Crossref Search in Google Scholar
1b Habusha U. Rozental E. Hoz S. J. Am. Chem. Soc. 2002, 124: 15006

Crossref Search in Google Scholar
2a McCoy L. J. Am. Chem. Soc. 1960, 82: 6416

Crossref Search in Google Scholar
2b Wendish D. In Houben-Weyl, Methoden der organischen Chemie Vol. IV 3: , Thieme; Stuttgart: 1971. p.89

Crossref Search in Google Scholar
2c Fleming FF. Shook BC. Tetrahedron 2002, 58: 1

Crossref Search in Google Scholar
3 Zwanenburg B. De Kimpe N. In Houben-Weyl, Methoden der organischen Chemie Vol. E17a: Thieme; Stuttgart: 1997. p.45

Search in Google Scholar
4 Mann J. Comprehensive Organic Synthesis Vol. 3: Trost B. Pergamon; Oxford: 1991. p.839

Search in Google Scholar
5a Paquette LA. Org. React. 1971, 25: 1

Search in Google Scholar
5b Clough JM. Comprehensive Organic Synthesis Vol. 3: Trost B. Pergamon; Oxford: 1991. p.861

Search in Google Scholar
6a Mkosza M. Przyborowski J. Klajn R. Kwast A. Synlett 2000, 1773
6b Mkosza M. Judka M. Chem.-Eur. J. 2002, 8: 4234

Search in Google Scholar
7a Collins SPW. Djuric W. Chem. Rev. 1993, 93: 1533

Search in Google Scholar
7b Mathew J. Recent Progress in the Chemical Synthesis of Antibiotics, Lucas G. Vol. II: Springer Verlag; Heidelberg: 1993. p.435

Search in Google Scholar
7c Mikolajczyk M. Mikina M. Jankowska A. J. Org. Chem. 2000, 65: 5127

Search in Google Scholar
7d Ghosh S. Patra D. Pure Appl. Chem. 1996, 68: 597

Search in Google Scholar
8 Hanselaer R. Samson M. Vandewalle M. Tetrahedron 1978, 34: 2393

Search in Google Scholar
9a Hudlicky T. Price JD. Chem. Rev. 1989, 89: 1467

Search in Google Scholar
9b Thebtaranonth C. Thebtaranonth Y. Tetrahedron 1990, 46: 1385

Search in Google Scholar
9c Survey of cyclopentane ring formation, see: Larock RL. Comprehensive Organic Transformations 2nd ed.: Wiley-VCH; New York: 1999. p.168-174

Search in Google Scholar
9d Du Y. Lu X. Zhang C. Angew. Chem. Int. Ed. 2003, 42: 1035

Search in Google Scholar
9e Huart C. Ghosez L. Angew. Chem., Int. Ed. Engl. 1997, 36: 634

Search in Google Scholar
10 Silva LF. Tetrahedron 2002, 58: 9137

Crossref Search in Google 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.