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Synthesis 2009(3): 409-423  
DOI: 10.1055/s-0028-1083324
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Bicyclo[3.1.0]hexan-2-ones by Manganese(III) Oxidation in Ethanol

Kentaro Asahia, Hiroshi Nishino*b
a Department of Materials and Life Sciences, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
b Department of Chemistry, Graduate School of Science and Technology, Kumamoto University, Kurokami, Kumamoto 860-8555, Japan
Fax: +81(96)3423374; e-Mail: nishino@sci.kumamoto-u.ac.jp;
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Publication History

Received 18 August 2008
Publication Date:
12 January 2009 (online)

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Abstract

N-Propenyl-3-oxobutanamides underwent the manganese(III)-induced oxidative intramolecular cyclization in ethanol to produce 3-azabicyclo[3.1.0]hexan-2-ones in good yields. A similar reaction of propenyl 3-oxobutanoates and S-propenyl 3-oxobutanethioates also gave the corresponding 3-oxa- and 3-thiabicy­clo[3.1.0]hexan-2-ones. The reaction details, the structure determination, and the reaction pathway are described.

Key words

cyclizations - oxidations - radical reactions - bicy­clo[3.1.0]hexanones - manganese(III) acetate

    References

  • 1a Gensini M. de Meijere A. Chem. Eur. J.  2004,  10:  785 ; and references cited therein
    Search in Google Scholar
  • 1b Machowicz-Stefaniak Z. Sadlo S. Rocz. Nauk Rolniczych, Seria E: Ochrona Roslin  1996,  25:  29 ; Chem. Abstr. 1996, 127, 274103
    Search in Google Scholar
  • 1c Donaldson WA. Tetrahedron  2001,  57:  8589 
    Search in Google Scholar
  • 1d Tobe Y. Yamashita D. Takahashi T. Inata M. Sato J. Kakiuchi K. Kobiro K. Odaira Y. J. Am. Chem. Soc.  1990,  112:  775 
    Search in Google Scholar
  • 1e Trost BM. Chung JYL. J. Am. Chem. Soc.  1985,  107:  4586 
    Search in Google Scholar
  • 1f Mulholland D. Mahomed H. Kotsos M. Randrianarivelojosia M. Lavaud C. Massiot G. Nuzillard J. Tetrahedron  1999,  55:  11547 
    Search in Google Scholar
  • 1g Renslo AR. Gao H. Jaishankar P. Venkatachalam R. Gomez M. Blais J. Huband M. Vara Prasad JVN. Gordeev MF. Bioorg. Med. Chem. Lett.  2006,  16:  1126 
    Search in Google Scholar
  • 1h Renslo AR. Gao H. Jaishankar P. Venkatachalam R. Gordeev MF. Org. Lett.  2005,  7:  2627 
    Search in Google Scholar
  • 2 Kavanagh F. Hervey A. Robbins WJ. Proc. Natl. Acad. Sci. U.S.A.  1949,  35:  343 
    CrossrefPubMedSearch in Google Scholar
  • 3a Ma S. Lu L. J. Org. Chem.  2005,  70:  7629 
    Search in Google Scholar
  • 3b Welbes LL. Lyons TW. Cychosz KA. Sanford MS. J. Am. Chem. Soc.  2007,  129:  5836 
    Search in Google Scholar
  • 3c Baldovini N. Bertrand MP. Carriére A. Nouguier R. Plancher JM. J. Org. Chem.  1996,  61:  3205 
    Search in Google Scholar
  • 3d Yang D. Yan Y.-L. Law K.-L. Zhu N.-Y. Tetrahedron  2003,  59:  10465 
    Search in Google Scholar
  • 3e Finta Z. Hell Z. Cwik A. Toke L. J. Chem. Res., Synop.  2002,  459 
  • 3f Gabbutt CD. Heron BM. Thomas DA. Light ME. Hursthouse MB. Tetrahedron Lett.  2004,  45:  6151 
    Search in Google Scholar
  • 3g Doyle MP. Hu W. ARKIVOC  2003,  (vii):  15 
    Search in Google Scholar
  • 3h Davies HML. Calvo RL. Townsend RJ. Ren P. Churchill RM. J. Org. Chem.  2000,  65:  4261 
    Search in Google Scholar
  • 3i Moody CJ. Miah S. Slawin AMZ. Mansfield DJ. Richards IC. J. Chem. Soc., Perkin Trans. 1.  1998,  4067 
  • 3j Nakano H. Ibata T. Bull. Chem. Soc. Jpn.  1995,  68:  1393 
    Search in Google Scholar
  • 3k Muller P. Bolea C. Helv. Chim. Acta  2001,  84:  1093 
    Search in Google Scholar
  • 3l Koskinen AMP. Munoz LJ. J. Org. Chem.  1993,  58:  879 
    Search in Google Scholar
  • 4a Asahi K. Nishino H. Heterocycl. Commun.  2005,  11:  379 
    Search in Google Scholar
  • 4b Asahi K. Nishino H. Tetrahedron  2005,  61:  11107 
    Search in Google Scholar
  • 4c Asahi K. Nishino H. Tetrahedron Lett.  2006,  47:  7259 
    Search in Google Scholar
  • 4d Asahi K. Nishino H. Tetrahedron  2006,  64:  1620 
    Search in Google Scholar
  • 4e Asahi K. Nishino H. Heterocycl. Commun.  2007,  14:  21 
    Search in Google Scholar
  • 4f Nishino H. Bull. Chem. Soc. Jpn.  1985,  58:  1922 
    Search in Google Scholar
  • 4g Tategami S. Yamada T. Nishino H. Korp JD. Kurosawa K. Tetrahedron Lett.  1990,  31:  6371 
    Search in Google Scholar
  • 4h Nishino H. Tategami S. Yamada T. Korp JD. Kurosawa K. Bull. Chem. Soc. Jpn.  1991,  64:  1800 
    Search in Google Scholar
  • 4i Nguyen V.-H. Nishino H. Kurosawa K. Tetrahedron Lett.  1997,  38:  1773 
    Search in Google Scholar
  • 4j Nguyen V.-H. Nishino H. Kurosawa K. Heterocycles  1998,  48:  465 
    Search in Google Scholar
  • 4k Chowdhury FA. Nishino H. Kurosawa K. Tetrahedron Lett.  1998,  39:  7931 
    Search in Google Scholar
  • 4l Chowdhury FA. Nishino H. Kurosawa K. Heterocycles  1999,  51:  575 
    Search in Google Scholar
  • 4m Kumabe R. Nishino H. Yasutake M. Nguyen V.-H. Kurosawa K. Tetrahedron Lett.  2001,  42:  69 
    Search in Google Scholar
  • 4n Qian C.-Y. Nishino H. Kurosawa K. J. Org. Chem.  1993,  58:  4448 
    Search in Google Scholar
  • 4o Rahman MT. Nishino H. Qian C.-Y. Tetrahedron Lett.  2003,  44:  5225 
    Search in Google Scholar
  • 4p Rahman MT. Nishino H. Org. Lett.  2003,  5:  2887 
    Search in Google Scholar
  • 4q Rahman MT. Nishino H. Tetrahedron  2003,  59:  8383 
    Search in Google Scholar
  • 4r Kumabe R. Nishino H. Tetrahedron Lett.  2004,  45:  703 
    Search in Google Scholar
  • 4s Kumabe R. Nishino H. Heterocycl. Commun.  2005,  10:  135 
    Search in Google Scholar
  • 4t Fujino R. Nishino H. Synthesis  2005,  731 
  • 5a Nguyen V.-H. Nishino H. Kurosawa K. Synthesis  1997,  899 
  • 5b Yamada T. Iwahara Y. Nishino H. Kurosawa K. J. Chem. Soc., Perkin Trans. 1  1993,  609 
  • 5c Nishino H. Nguyen V.-H. Yoshinaga S. Kurosawa K. J. Org. Chem.  1996,  61:  8264 
    Search in Google Scholar
  • 5d Bar G. Parsons AF. Thomas CB. Org. Biomol. Chem.  2003,  1:  373 
    Search in Google Scholar
  • 6a Snider BB. Chem. Rev.  1996,  96:  339 
    Search in Google Scholar
  • 6b Melikyan GG. Org. React.  1997,  49:  427 
    Search in Google Scholar
  • 6c Melikyan GG. Aldrichimica Acta  1998,  31:  50 
    Search in Google Scholar
  • 6d Nishino H. In Bioactive Heterocycles I   Eguchi S. Springer; Berlin: 2006.  p.39-76  
  • 6e Demir AS. Emrullahoglu M. Curr. Org. Synth.  2007,  4:  321 
    Search in Google Scholar
  • 7a Oumar-Mahamat H. Moustrou C. Surzur JM. Bertrand MP. Tetrahedron Lett.  1989,  30:  331 
    Search in Google Scholar
  • 7b Oumar-Mahamat H. Moustrou C. Surzur JM. Bertrand MP. J. Org. Chem.  1989,  54:  5684 
    Search in Google Scholar
  • 7c Galeazzi R. Geremia S. Mobbili G. Orena M. Tetrahedron: Asymmetry  1996,  7:  3573 
    Search in Google Scholar
  • 7d Swain NA. Brown RCD. Bruton G. Chem. Commun.  2002,  2042 
  • 7e Skerry PS. Swain NA. Harrowven DC. Smyth D. Bruton G. Brown RCD. Chem. Commun.  2004,  1772 
  • 7f Swain NA. Brown RCD. Bruton G. J. Org. Chem.  2004,  69:  122 
    Search in Google Scholar
  • 7g Snider BB. Merritt JE. Dombroski MA. Buckman BO. J. Org. Chem.  1991,  56:  5544 
    Search in Google Scholar
  • 7h Snider BB. McCarthy BA. J. Org. Chem.  1993,  58:  6217 
    Search in Google Scholar
  • 8 Waldemar A. Rebollo H. Rosenthal RJ. Peters EM. Peters K. Von Schnering HG. Chem. Ber.  1984,  117:  2393 
    CrossrefSearch in Google Scholar
  • 9a

    Actually, it is known that the Mn(OAc)3 consists of an oxygen-centered trinuclear complex, which is relatively stable in AcOH. However, when the oxidation was conducted in other solvents, such as EtOH, the trinuclear structure of Mn(III) might be deformed and the oxidizing ability weakened.

  • 9b de Klein WJ. In Organic Syntheses by Oxidation with Metal Compounds   Mijs WJ. de Jonge CRHI. Plenum; New York: 1986.  p.261-314  
  • 9c Anderson JM. Kochi JK. J. Am. Chem. Soc.  1970,  92:  2450 
    Search in Google Scholar
  • 10 Rosenberg SH. Rapoport H. J. Org. Chem.  1985,  50:  3979 
    CrossrefSearch in Google Scholar
  • 11 Yagi H. Thakker DR. Lehr RE. Jerina DM. J. Org. Chem.  1979,  44:  3442 
    CrossrefSearch in Google Scholar
  • 12a Smith AB. Friestad GK. Barbosa J. Bertounesque E. Duan JJ.-W. Hull KG. Iwashima M. Qiu Y. Spoors PG. Salvatore BA. J. Am. Chem. Soc.  1999,  121:  10478 
    Search in Google Scholar
  • 12b Gao Z.-G. Kim S.-K. Biadatti T. Chen W. Lee K. Barak D. Kim SG. Johnson CR. Jacobson KA. J. Med. Chem.  2002,  45:  4471 
    Search in Google Scholar
  • 13 Jogo S. Nishino H. Yasutake M. Shinmyozu T. Tetrahedron Lett.  2002,  43:  9031 
    CrossrefSearch in Google Scholar
  • 16 Zhou C.-Y. Che C.-M. J. Am. Chem. Soc.  2007,  129:  5828 
    CrossrefSearch in Google Scholar
  • 17 Simes BE. Rickborn B. Flournoy JM. Berlman IB. J. Org. Chem.  1988,  53:  4613 
    CrossrefSearch in Google Scholar
  • 18 Le Tadic-Biadatti M.-H. Callier-Dublanchet A.-C. Horner JH. Quiclet-Sire B. Zard SZ. Newcomb M. J. Org. Chem.  1997,  62:  559 
    Search in Google Scholar
  • 19a Zhao W, and Carreira EM. inventors; PCT Int. Appl.  WO03057679.  ; Chem. Abstr. 2003, 138, 239391
  • 19b Van der Bent A. Blommaert AGS. Melman CTM. IJzerman AP. Van Wijngaarden I. Soudijn W. J. Med. Chem.  1992,  35:  1042 
    Search in Google Scholar
  • 20 Makino T. Itoh K. J. Org. Chem.  2004,  69:  395 
    Search in Google Scholar
  • 21 Sunakawa J, Sasaki A, and Shimako K. inventors; Jpn. Kokai Tokkyo Koho  05262696.  ; Chem. Abstr. 1993, 120, 191131
  • 22 Aoyama T. Takido T. Kodomari M. Synth. Commun.  2003,  33:  3817 
    CrossrefSearch in Google Scholar
14

The oxidation of 1l,m only with Mn(OAc)3 gave 2l,m in 60, 48, and 37% yield, respectively. Compare these with the yields described in Table  [¹] , entries 15-17.

15

The most stable conformation of 3,4-trans-pyrrolidinone 3a was calculated to be -310.0 kJ/mol by Spartan ’06 based on the PM3 parameter. The calculated dihedral angle between H-3 and H-4 was 128.9˚. On the other hand, the 3,4-cis 3a was -293.1 kJ/mol and the dihedral angle was 27.3˚.