Synthetic Studies on the MARDi Cascade: Stereoselective Preparation of Sulfonyl-Substituted Seven-Membered Rings

Abstract

A stereoselective synthesis of functionalized sulfonyl-substituted cycloheptanes is described. The approach involves a ­formal two-carbon ring expansion of 2-benzenesulfonyl cyclopentanones through a base-induced anionic domino three-component transformation named the MARDi cascade.

Key words

stereoselective synthesis - domino reactions - multi-component reactions - ring expansion - cycloheptane

References and Notes

• 1a Rodriguez J. Synlett  1999,  505 
• 1b Simon C. Constantieux T. Rodriguez J. Eur. J. Org. Chem.  2004,  4957 
• 1c Liéby-Muller F. Simon C. Constantieux T. Rodriguez J. QSAR Comb. Sci.  2006,  25:  432 
• 2a Filippini M.-H. Rodriguez J. Santelli M. J. Chem. Soc., Chem. Commun.  1993,  1647 
• 2b Filippini M.-H. Rodriguez J. J. Org. Chem.  1997,  62:  3034 
• 2c

  The structure of the cycloheptenic acids 3 has been reviewed and confirmed to be as depicted in Scheme [1] by X-ray diffraction analysis of the derivative A (Scheme [3] ; see ref. 9). The full detailed study of the MARDi cascade will be reported in due time.

• 3a Filippini M.-H. Rodriguez J. Chem. Rev.  1999,  99:  27 
• 3b Filippini M.-H. Faure R. Rodriguez J. J. Org. Chem.  1995,  60:  6872 
• For reviews, see:
• 4a Yet L. Tetrahedron  1999,  55:  9349 
• 4b Yet L. Chem. Rev.  2000,  100:  2963 
• 4c Kantorowski EJ. Kurth MJ. Tetrahedron  2000,  56:  4317 
• 4d Maier ME. Angew. Chem. Int. Ed.  2000,  39:  2073 
• For examples of sulfonyl-substituted cycloheptanes, see:
• 4e Arjona O. de Dios A. Fernández de la Pradilla R. Plumet J. Viso A. J. Org. Chem.  1994,  59:  3906 
• 4f Arjona O. Plumet J. Curr. Org. Chem.  2002,  6:  571 
• 4g El-Awa A. Fuchs P. Org. Lett.  2006,  8:  2905 
• 5 Trost BM. Salzmann TN. Hiroi K. J. Am. Chem. Soc.  1976,  98:  4887 
• 6 Carreño MC. García Ruano JL. Pedregal C. Rubio A. J. Chem. Soc., Perkin Trans. 1  1989,  1335 
• 7 Kraus GA. Hansen J. Vines D. Synth. Commun.  1992,  22:  2625 
• 8 Hashimoto N. Aoyama T. Shiori T. Chem. Pharm. Bull.  1981,  29:  1475 

9

Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, with CCDC numbers 615710, 615708, 615709 for com­-pounds A, 8 and 9, respectively. Copies of this information can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [Fax: [phone]; E-mail: [e-mail] or www: http://www.ccdc.cam.ac.uk].