Download PDF
Synlett 2011(16): 2275-2278  
DOI: 10.1055/s-0030-1261226
SYNPACTS
© Georg Thieme Verlag Stuttgart ˙ New York

N-Heterocyclic Carbene (NHC)-Catalyzed All-Carbon [4+2] Cycloaddition-Decarboxylation

Sarah Ryan, Lisa Candish, David W. Lupton*
Monash University, School of Chemistry, Clayton 3800, Victoria, Australia
Fax: +61(3)99054597; e-Mail: david.lupton@monash.edu;
Further Information

Publication History

Received 24 July 2011
Publication Date:
08 September 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

NHCs activate a diverse range of materials and thereby play a central role in modern reaction discovery. Our studies have focused on the application of NHCs as Lewis base catalysts. We recently developed an all-carbon [4+2] cycloaddition-decarboxylation that typifies this type of catalysis. Herein, the discovery of this methodology, its context and scope are discussed.

Key words

catalysis - acyl azolium - N-heterocyclic carbenes - cycloaddition - cyclohexadiene

    References

  • 1 Ugai T. Tanaka S. Dokawa S. J. Pharm. Soc. Jpn.  1943,  63:  296 
    Google Scholar
  • 2 Breslow R. J. Am. Chem. Soc.  1958,  80:  3719 
    Google Scholar
  • For reviews on NHC catalysis, see:
  • 3a Enders D. Niemeier O. Henseler A. Chem. Rev.  2007,  107:  5606 
    Google Scholar
  • 3b Marion N. Díez-González S. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2988 
    Google Scholar
  • 3c Nair V. Vellalath S. Babu BP. Chem. Soc. Rev.  2008,  37:  2691 
    Google Scholar
  • 3d Moore JL. Rovis T. Top. Curr. Chem.  2009,  290:  77 
    Google Scholar
  • 3e Phillips EM. Chan A. Scheidt KA. Aldrichimica Acta  2009,  42:  55 
    Google Scholar
  • 3f Vora HH. Rovis T. Aldrichimica Acta  2011,  44:  3 
    Google Scholar
  • 4 Castells J. Llitjos H. Moreno-Mañas M. Tetrahedron Lett.  1977,  18:  205 
    CrossrefGoogle Scholar
  • For examples with cyanide, see:
  • 5a Corey EJ. Gilman NW. Ganem RE. J. Am. Chem. Soc.  1968,  90:  5616 
    Google Scholar
  • 5b Corey EJ. Katzenellenbogen JA. Gilman NW. Roman SA. Erickson BW. J. Am. Chem. Soc.  1968,  90:  5618 
    Google Scholar
  • For other examples of oxidations of acyl anions to acyl azoliums, see:
  • 6a Ohta S. Hayakawa S. Nishimura K. Okamoto M. Chem. Pharm. Bull.  1987,  135:  1058 
    Google Scholar
  • 6b Miyashita A. Suzuki Y. Nagasaki I. Iwamoto K.-I. Higashino T. Chem. Pharm. Bull.  1997,  45:  1254 
    Google Scholar
  • For examples of acyl azolium catalysis, see:
  • 7a Chow KY.-K. Bode JW. J. Am. Chem. Soc.  2004,  126:  8126 
    Google Scholar
  • 7b Reynolds NT. ReaddeAlaniz J. Rovis T. J. Am. Chem. Soc.  2004,  126:  9518  
    Google Scholar
  • For selected studies involving acyl azoliums, see:
  • 7c Burstein C. Glorius F. Angew. Chem. Int. Ed.  2004,  43:  6205 
    Google Scholar
  • 7d Sohn SS. Rosen EL. Bode JW. J. Am. Chem. Soc.  2004,  126:  14370 
    Google Scholar
  • 7e Chan A. Scheidt KA. Org. Lett.  2005,  7:  905 
    Google Scholar
  • 7f Zeitler K. Org. Lett.  2006,  8:  637 
    Google Scholar
  • 7g Maki BE. Chan A. Phillips EM. Scheidt KA. Org. Lett.  2007,  9:  371 
    Google Scholar
  • 7h Vora HU. Rovis T. J. Am. Chem. Soc.  2007,  129:  13796 
    Google Scholar
  • 7i Guin J. De Sarkar S. Grimme S. Studer A. Angew. Chem. Int. Ed.  2008,  47:  8727 
    Google Scholar
  • 7j Maki BE. Patterson EV. Cramer CJ. Scheidt KA. Org. Lett.  2009,  11:  3942 
    Google Scholar
  • 7k Philips EM. Wadamoto M. Roth HS. Ott AW. Scheidt KA. Org. Lett.  2009,  11:  105 
    Google Scholar
  • 7l Vora HU. Rovis T. J. Am. Chem. Soc.  2010,  132:  2860 
    Google Scholar
  • 7m De Sarkar S. Grimme S. Studer A. J. Am. Chem. Soc.  2010,  132:  1190 
    Google Scholar
  • 7n Thai K. Wang L. Dudding T. Bilodeau F. Gravel M. Org. Lett.  2010,  12:  5708 
    Google Scholar
  • 7o De Sarkar S. Studer A. Org. Lett.  2010,  12:  1992 
    Google Scholar
  • 7p De Sarkar S. Biswas A. Song CH. Studer A. Synthesis  2011,  1974 
    Google Scholar
  • 8For a review on Lewis base catalysis, see:
  • 8 Denmark SE. Beutner GL. Angew. Chem. Int. Ed.  2008,  47:  1560 
    CrossrefPubMedGoogle Scholar
  • For reviews on NHC nucleophilicity, see:
  • 9a Mayr H. Breugst M. Maji B. Angew. Chem. Int. Ed.  2011,  50:  6915 
    Google Scholar
  • 9b Dröge T. Glorius F. Angew. Chem. Int. Ed.  2010,  49:  6940 
    Google Scholar
  • 10For the Mukaiyama aldol reaction, see:
  • 10 Song JJ. Tan Z. Reeves JT. Yee NK. Senanayake CH. Org. Lett.  2007,  9:  1013; for other examples of C-Si activation, see articles cited therein 
    Google Scholar
  • 11 Lee K.-S. Zhugralin AR. Hoveyda AH. J. Am. Chem. Soc.  2009,  131:  7253 
    Google Scholar
  • 12a Fischer C. Smith SW. Powell DA. Fu GC. J. Am. Chem. Soc.  2006,  128:  1472  For recent extentions of this type of reactivity, see: Matsuoka SI. Ota Y. Washio A. Katada A. Ichioka K. Takagi K. Suzuki M. Org. Lett.  2011,  13:  3722 
    Google Scholar
  • 12b Biju AT. Padmanaban M. Wurz NE. Glorius F. Angew. Chem. Int. Ed.  2011,  50:  DOI: 10.1002/anie.201103555 
  • 13a Grasa GA. Kissling RM. Nolan SP. Org. Lett.  2002,  4:  3583 
    Google Scholar
  • 13b Nyce GW. Lamboy JA. Connor EF. Waymouth RM. Hedrick JL. Org. Lett.  2002,  4:  3587 
    Google Scholar
  • NHC-catalyzed transesterification with amino alcohols and mechanistic comments:
  • 13c Movassaghi M. Schmidt MA. Org. Lett.  2005,  7:  2453 
    Google Scholar
  • 13d Schmidt MA. Müller P. Movassaghi M. Tetrahedron Lett.  2008,  49:  4316 
    Google Scholar
  • 14 Song JJ. Tan Z. Reeves JT. Fandrick DR. Yee NK. Senanayake CH. Org. Lett.  2008,  10:  877 
    CrossrefPubMedGoogle Scholar
  • 15a Ryan SJ. Candish L. Lupton DW. J. Am. Chem. Soc.  2009,  131:  14176 
    Google Scholar
  • 15b Candish L. Lupton DW. Org. Lett.  2010,  12:  4836 
    Google Scholar
  • For a related reaction with mechanistic discussion, see:
  • 16a Kaeobamrung J. Mahatthananchai J. Zheng P. Bode JW. J. Am. Chem. Soc.  2010,  132:  8810 
    Google Scholar
  • 16b Mahatthananchai J. Zheng P. Bode JW. Angew. Chem. Int. Ed.  2011,  50:  1673 
    Google Scholar
  • For related reactions, see:
  • 17a De Sarkar S. Studer A. Angew. Chem. Int. Ed.  2010,  49:  9266 
    Google Scholar
  • 17b Zhu Z.-Q. Xiao J.-C. Adv. Synth. Catal.  2010,  352:  2455 
    Google Scholar
  • 17c Zhu Z.-Q. Zheng X.-L. Jiang N.-F. Wan X. Xiao J.-C. Chem. Commun.  2011,  47:  8670 
    Google Scholar
  • 17d Rong Z.-Q. Jia M.-Q. You S.-L. Org. Lett.  2011,  13:  4080 
    Google Scholar
  • 18 Bappert E. Müller P. Fu G. Chem. Commun.  2006,  2604 
    Google Scholar
  • 19 Poisson T. Dalla V. Papamicaël C. Dupas G. Marsais F. Levacher V. Synlett  2007,  381 
    Google Scholar
  • 20 Woods PA. Morrill LC. Lebl T. Slawin AMZ. Bragg RA. Smith AD. Org. Lett.  2010,  12:  2660 
    CrossrefGoogle Scholar
  • For NHC-catalyzed reactions involving β-lactones, see:
  • 21a Nair V. Vellalath S. Poonoth M. Suresh E. J. Am. Chem. Soc.  2006,  128:  8736 
    Google Scholar
  • 21b Chiang P.-C. Kaeobamrung J. Bode JW. J. Am. Chem. Soc.  2007,  129:  3520 
    Google Scholar
  • 21c Wadamoto M. Phillips EM. Reynolds TE. Scheidt KA. J. Am. Chem. Soc.  2007,  129:  10098 
    Google Scholar
  • 21d He M. Bode JW. J. Am. Chem. Soc.  2008,  130:  418 
    Google Scholar
  • 21e Kaeobamrung J. Bode JW. Org. Lett.  2009,  11:  677 
    Google Scholar
  • 21f Phillips EM. Roberts JM. Scheidt KA. Org. Lett.  2010,  12:  2830 
    Google Scholar
  • For a useful review on 2-pyrones and 2-pyridones in synthesis, see:
  • 22a Afarinkia K. Vinader V. Nelson TD. Posner GH. Tetrahedron  1992,  48:  9111 
    Google Scholar
  • For recent examples in catalysis, see:
  • 22b Soh JY.-T. Tan CH.
    J. Am. Chem. Soc.  2009,  131:  6904 
    Google Scholar
  • For selected studies in total synthesis, see:
  • 22c Martin SF. Rüeger H. Williamson SA. Grzejszczak S. J. Am. Chem. Soc.  1987,  109:  6124 
    Google Scholar
  • 22d Nelson HM. Stoltz BM. Org. Lett.  2008,  10:  25 
    Google Scholar
  • 22e Baran PS. Burns NZ. J. Am. Chem. Soc.  2006,  128:  3908 
    Google Scholar
  • For methodologies, see:
  • 22f Li L. Chase CE. West FG. Chem. Commun.  2008,  4025 
    Google Scholar
  • 22g Afarinkia K. Abdullahi MH. Scowen IJ. Org. Lett.  2010,  12:  5564 
    Google Scholar
  • 23 Ryan SJ. Candish L. Lupton DW. J. Am. Chem. Soc.  2011,  133:  4694 
    Google Scholar
  • 25For a review on vinylogous reactivity, see:
  • 25 Denmark SE. Heemstra JR. Beutner GL. Angew. Chem. Int. Ed.  2005,  44:  4682 
    CrossrefGoogle Scholar
24

Ryan, S. J.; Paddon-Row, M. Lupton, D. W. unpublished results.