Synlett 2013; 24(4): 483-486
DOI: 10.1055/s-0032-1318168
letter
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of Cyclopropanecarboxylic Acid Esters Starting from the Conjugate Addition of Lithium Ester Enolates to 1-Chlorovinyl p-Tolyl ­Sulfoxides

Tsutomu Kimura
a   Department of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
,
Yoshiaki Hattori
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   eMail: tsatoh@rs.kagu.tus.ac.jp
,
Hitoshi Momochi
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   eMail: tsatoh@rs.kagu.tus.ac.jp
,
Nobuhito Nakaya
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   eMail: tsatoh@rs.kagu.tus.ac.jp
,
Tsuyoshi Satoh*
a   Department of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   eMail: tsatoh@rs.kagu.tus.ac.jp
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Publikationsverlauf

Received: 20. Dezember 2012

Accepted after revision: 15. Januar 2013

Publikationsdatum:
29. Januar 2013 (online)


Abstract

An efficient synthesis of tert-butyl cyclopropanecarboxylates was achieved in three steps using 1-chlorovinyl p-tolyl sulfoxides as key materials. The conjugate addition of lithium ester enolates to the sulfoxides gave tert-butyl 4-chloro-4-(p-tolylsulfinyl)butanoates in high yield. The p-tolylsulfinyl group in the resultant adducts was then removed by the sulfoxide–magnesium exchange reaction with i-PrMgCl at –60 °C. Cyclization of the desulfinylated products, tert-butyl 4-chlorobutanoates, took place in the presence of NaHMDS in a THF–DMPU mixture to afford tert-butyl cyclopropanecarboxylates in good yield. The asymmetric synthesis of both enantiomers of tert-butyl cyclopropanecarboxylate was successfully achieved using optically active (E)- and (Z)-sulfoxides with high enantiomeric excesses.

Supporting Information

 
  • References and Notes

    • 1a Wong HN. C, Hon M.-Y, Tse C.-W, Yip Y.-C, Tanko J, Hudlicky T. Chem. Rev. 1989; 89: 165
    • 1b Reissig H.-U, Zimmer R. Chem. Rev. 2003; 103: 1151
    • 1c Yu M, Pagenkopf BL. Tetrahedron 2005; 61: 321
    • 3a Donaldson WA. Tetrahedron 2001; 57: 8589
    • 3b Chen DY.-K, Pouwer RH, Richard J.-A. Chem. Soc. Rev. 2012; 41: 4631
    • 4a Salaün J. Chem. Rev. 1989; 89: 1247
    • 4b Doyle MP, Protopopova MN. Tetrahedron 1998; 54: 7919
    • 4c Lebel H, Marcoux J.-F, Molinaro C, Charette AB. Chem. Rev. 2003; 103: 977
    • 4d Pellissier H. Tetrahedron 2008; 64: 7041
    • 5a Satoh T. Chem. Rec. 2004; 3: 329
    • 5b Satoh T. Chem. Soc. Rev. 2007; 36: 1561
    • 5c Satoh T. Heterocycles 2012; 85: 1
    • 5d Satoh T In The Chemistry of Organomagnesium Compounds . Rappoport Z, Marek I. John Wiley and Sons; Chichester: 2008: 717-769
    • 6a Satoh T, Musashi J, Kondo A. Tetrahedron Lett. 2005; 46: 599
    • 6b Miyagawa T, Tatenuma T, Tadokoro M, Satoh T. Tetrahedron 2008; 64: 5279
    • 6c Ogata S, Saitoh H, Wakasugi D, Satoh T. Tetrahedron 2008; 64: 5711
    • 6d Watanabe H, Ogata S, Satoh T. Tetrahedron 2010; 66: 5675
    • 6e Satoh T, Kuramoto T, Ogata S, Watanabe H, Saitou T, Tadokoro M. Tetrahedron: Asymmetry 2010; 21: 1 ; and references cited therein
    • 7a Satoh T, Sugiyama S, Kamide Y, Ota H. Tetrahedron 2003; 59: 4327
    • 7b Sugiyama S, Satoh T. Tetrahedron: Asymmetry 2005; 16: 665
    • 7c Kido M, Sugiyama S, Satoh T. Tetrahedron: Asymmetry 2007; 18: 1934
    • 7d Sugiyama S, Nakaya N, Satoh T. Tetrahedron: Asymmetry 2008; 19: 401
  • 8 Synthesis of tert-Butyl 4-Chloro-4-(p-tolylsulfinyl)butanoates 3 – Typical Procedure A 1.65 M solution of BuLi in hexane (9.09 mL, 15.0 mmol) was added to a solution of i-Pr2NH (1.52 g, 15.0 mmol) in THF (55 mL) at 0 °C, and the mixture was stirred at that temperature for 10 min. tert-Butyl propionate (2a, 1.95 g, 15.0 mmol) was added dropwise to the solution at –78 °C, and the mixture was stirred at that temperature for 10 min. A solution of sulfoxide 1a (806 mg, 3.00 mmol) in THF (5 mL) was added to the resulting solution at –78 °C, and the reaction mixture was stirred at that temperature for 5 min. The reaction was quenched with sat. aq NH4Cl (5 mL), and the mixture was extracted with CHCl3 (3 × 80 mL). The organic layer was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel [Rf  = 0.51 (hexane–EtOAc = 2:1)] to give 3a as a colorless oil; yield 1.18 g (2.97 mmol, 99%).
  • 9 Synthesis of tert-Butyl 4-Chlorobutanoates 6 – Typical Procedure A solution of 3a (978 mg, 2.45 mmol) in THF (10 mL) was added dropwise to a 75.9 mM solution of i-PrMgCl in THF (113 mL, 8.58 mmol) at –60 °C, and the reaction mixture was stirred at that temperature for 5 min. The reaction was quenched with sat. aq NH4Cl (5 mL), and the mixture was extracted with CHCl3 (3 × 80 mL). The organic layer was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel [Rf  = 0.54 (hexane–EtOAc = 10:1] to give 6a as a colorless oil; yield 594 mg (2.28 mmol, 93%).
    • 10a Russell GA, Makosza M, Hershberger J. J. Org. Chem. 1979; 44: 1195
    • 10b Lantzsch R. Synthesis 1982; 955
    • 10c Anzalone L, Hirsch JA. J. Org. Chem. 1985; 50: 2128
    • 10d Matsui K, Negishi A, Takahatake Y, Sugimoto K, Fujimoto T, Takashima T, Kondo K. Bull. Chem. Soc. Jpn. 1986; 59: 221
  • 11 Mukhopadhyay T, Seebach D. Helv. Chim. Acta 1982; 65: 385
  • 12 Synthesis of tert-Butyl Cyclopropanecarboxylates 7 – Typical Procedure A 1.9 M solution of NaHMDS in THF (0.082 mL, 0.16 mmol) was added dropwise to a solution of 6a (27.2 mg, 0.104 mmol) in a THF–DMPU mixture (0.52 mL/0.52 mL) at 0 °C, and the reaction mixture was stirred at r.t. for 28 h. The reaction was quenched with sat. aq NH4Cl (0.5 mL), and the mixture was extracted with toluene (3 × 8 mL). The organic layer was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel [Rf  = 0.51 (hexane–EtOAc = 10:1] to give 7a as a colorless oil; yield 22.5 mg (0.100 mmol, 96%).
  • 13 Brackmann F, De Meijere A. Chem. Rev. 2007; 107: 4493
    • 14a Lyle MP. A, Wilson PD. Org. Lett. 2004; 6: 855
    • 14b Suematsu H, Kanchiku S, Uchida T, Katsuki T. J. Am. Chem. Soc. 2008; 130: 10327
    • 14c Ito J, Ujiie S, Nishiyama H. Chem. Eur. J. 2010; 16: 4986