Bidentate Lewis Acid Catalyzed Inverse-Electron-Demand Diels–Alder Reaction for the Selective Functionalization of Aldehydes

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

The inverse-electron-demand Diels–Alder (IEDDA) reaction catalyzed by a bidentate Lewis acid was applied to enamines generated in situ from aldehydes. In general, a high functional group tolerance has been observed. Side reactions during the enamine forming step can limit the yield of the desired naphthalene. For citronellal as substrate, the initial intermediate after the catalyzed IEDDA reaction was trapped by an intramolecular Diels–­Alder reaction to furnish a tricyclic compound. This scaffold represents the framework of natural products such as valerianoids A–C or the patchouli alcohol.

• References

• 1a Dobson CM. Nature 2004; 432: 824
  CrossrefSearch in Google Scholar
• 1b Lipinski C, Hopkins A. Nature 2004; 432: 855
  CrossrefSearch in Google Scholar
• 1c Reymond J.-L, Van Deursen R, Blum LC, Ruddigkeit L. Med. Chem. Commun. 2010; 1: 30
  CrossrefSearch in Google Scholar
• 2a Newman DJ, Cragg GM. J. Nat. Prod. 2007; 70: 461
  CrossrefPubMedSearch in Google Scholar
• 2b Cordier C, Morton D, Murrison S, Nelson A, O’leary-Steele C. Nat. Prod. Rep. 2008; 25: 719
  CrossrefPubMedSearch in Google Scholar
• 2c Grabowski K, Baringhaus K.-H, Schneider G. Nat. Prod. Rep. 2008; 25: 892
  CrossrefPubMedSearch in Google Scholar
• 3a Nicolaou KC, Vourloumis D, Winssinger N, Baran PS. Angew. Chem. Int. Ed. 2000; 39: 44
  CrossrefSearch in Google Scholar
• 3b Wilson RM, Danishefsky SJ. Angew. Chem. Int. Ed. 2010; 49: 6032
  CrossrefSearch in Google Scholar
• 4a Wilson RM, Danishefsky SJ. J. Org. Chem. 2006; 71: 8329
  CrossrefPubMedSearch in Google Scholar
• 4b Kumar K, Waldmann H. Angew. Chem. Int. Ed. 2009; 48: 3224
  CrossrefPubMedSearch in Google Scholar
• 4c Wetzel S, Bon RS, Kumar K, Waldmann H. Angew. Chem. Int. Ed. 2011; 50: 10800
  CrossrefPubMedSearch in Google Scholar
• 5a Hoffmann R. Synthesis 2006; 3531
  Thieme Connect
• 5b Young IS, Baran PS. Nat. Chem. 2009; 1: 193
  CrossrefPubMedSearch in Google Scholar
• 5c Shenvi RA, O’Malley DP, Baran PS. Acc. Chem. Res. 2009; 42: 530
  CrossrefSearch in Google Scholar
• 6a Nicolaou KC, Snyder SA, Montagnon T, Vassilikogiannakis G. Angew. Chem. Int. Ed. 2002; 41: 1668
  CrossrefPubMedSearch in Google Scholar
• 6b Kobayashi S, Jørgensen KA. Cycloaddition Reactions in Organic Synthesis. Wiley-VCH; Weinheim: 2002
  Search in Google Scholar
• 6c Takao K, Munakata R, Tadano K. Chem. Rev. 2005; 105: 4779
  CrossrefPubMedSearch in Google Scholar
• 6d Juhl M, Tanner D. Chem. Soc. Rev. 2009; 38: 2983
  CrossrefPubMedSearch in Google Scholar

For selected examples, see:
• 7a Boger DL, Coleman RS. J. Am. Chem. Soc. 1987; 109: 2717
  CrossrefSearch in Google Scholar
• 7b Boger DL, Zhang M. J. Am. Chem. Soc. 1991; 113: 4230
  CrossrefSearch in Google Scholar
• 7c Bodwell GJ, Li J. Angew. Chem. Int. Ed. 2002; 41: 3261
  CrossrefSearch in Google Scholar
• 8a Gruseck U, Heuschmann M. Tetrahedron Lett. 1987; 28: 6027
  CrossrefSearch in Google Scholar
• 8b For intramolecular examples, see: Boger DL, Coleman RS. J. Org. Chem. 1984; 49: 2240
  CrossrefSearch in Google Scholar
• 8c See also: Boger DL, Sakya SM. J. Org. Chem. 1988; 53: 1415
  CrossrefSearch in Google Scholar
• 8d For examples with phthalazines, see: Oishi E, Taido N, Iwamoto K, Miyashita A, Higashino T. Chem. Pharm. Bull. 1990; 38: 3268
  CrossrefSearch in Google Scholar
• 9a Kessler SN, Wegner HA. Org. Lett. 2010; 12: 4062
  CrossrefPubMedSearch in Google Scholar
• 9b Kessler SN, Neuburger M, Wegner HA. Eur. J. Org. Chem. 2011; 3238
• 9c Wegner HA, Kessler SN. Synlett 2012; 699
  Thieme Connect
• 10 Fernández Sainz Y, Raw SA, Taylor RJ. K. J. Org. Chem. 2005; 70: 10086
  CrossrefSearch in Google Scholar
• 11a Chavan SP, Dhondge VD, Patil SS, Rao YT. S, Govande CA. Tetrahedron: Asymmetry 1997; 8: 2517
  CrossrefSearch in Google Scholar
• 11b Schmalz HG, de Koning CB, Bernicke D, Siegel S, Pfletschinger A. Angew. Chem. Int. Ed. 1999; 38: 1620
  CrossrefSearch in Google Scholar
• 11c Hagiwara H, Okabe T, Ono H, Kamat VP, Hoshi T, Suzuki T, Ando M. J. Chem. Soc., Perkin Trans. 1 2002; 895
• 11d Mori K. Tetrahedron: Asymmetry 2005; 16: 685
  CrossrefSearch in Google Scholar
• 11e Kraus GA, Jeon I. Org. Lett. 2006; 8: 5315
  CrossrefSearch in Google Scholar
• 12 For a detailed assignment of the structure, see Supporting Information
• 13a Srikrishna A, Satyanarayana G. Org. Lett. 2004; 6: 2337
  CrossrefPubMedSearch in Google Scholar
• 13b Fukushima M, Morii A, Hoshi T, Suzuki T, Hagiwara H. Tetrahedron 2007; 63: 7154
  CrossrefSearch in Google Scholar
• 14a Näf F, Ohloff G. Helv. Chim. Acta 1974; 57: 1868
  CrossrefSearch in Google Scholar
• 14b Yamada K, Kyotani Y, Manabe S, Suzuki M. Tetrahedron 1979; 35: 293
  CrossrefSearch in Google Scholar
• 14c Magee TV, Stork G, Fludzinski P. Tetrahedron Lett. 1995; 36: 7607
  CrossrefSearch in Google Scholar
• 14d Srikrishna A, Satyanarayana G. Tetrahedron: Asymmetry 2005; 16: 3992
  CrossrefSearch in Google Scholar
• 15 Jagdale AR, Park JH, Youn SW. J. Org. Chem. 2011; 76: 7204
  CrossrefSearch in Google Scholar
• 16 Guan B.-T, Xiang S.-K, Wang B.-Q, Sun Z.-P, Wang Y, Zhao K.-Q, Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 3268
  CrossrefSearch in Google Scholar
• 17 Baroudi A, Mauldin J, Alabugin IV. J. Am. Chem. Soc. 2010; 132: 967
  CrossrefSearch in Google Scholar
• 18 Cho C.-H, Sun M, Seo Y.-S, Kim C.-B, Park K. J. Org. Chem. 2005; 70: 1482
  CrossrefSearch in Google Scholar
• 19 Guam B.-T, Xiang S.-K, Wang B.-Q, Sum Z.-P, Wang Y, Zhao K.-Q, Shi Z.-J. J. Am. Chem. Soc. 2008; 130: 3268
  CrossrefSearch in Google Scholar

• Supplementary Material