PDF icon Download PDF
Synlett 2011(9): 1243-1246  
DOI: 10.1055/s-0030-1259955
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Synthesis of Quinolizidines and Indolizidines via a Catalytic Asymmetric Hydrogenation Cascade

Magnus Rueping*, Lukas Hubener
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092665; e-Mail: magnus.rueping@rwth-aachen.de;
Further Information

Publication History

Received 31 January 2011
Publication Date:
18 April 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

A catalytic enantioselective synthesis of a new class of quinolizidines and indolizidines is presented. An asymmetric Brønsted acid catalyzed hydrogenation cascade as well as a sequential Brønsted acid/metal catalyzed hydrogenation protocol of 2-substituted quinolines yields benzofused quinolizidines and indolizidines in good yields with high diastereo- and enantioselectivities.

Key words

organocatalysis - domino reaction - amines - asymmetric reduction - Hantzsch ester

    References and Notes

  • 1a Pellisier H. Recent Developments in Asymmetric Organocatalysis   RSC; Cambridge: 2010. 
  • For a recent review, see:
  • 1b Buckley BR. Neary SP. Annu. Rep. Prog. Chem., Sect. B: Org. Chem.  2010,  106:  120 ; and references therein
    Search in Google Scholar
  • Other selected reviews:
  • 1c MacMillan DWC. Nature (London)  2008,  455:  304 
    Search in Google Scholar
  • 1d Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 ; Angew. Chem. 2008, 120, 4716
    Search in Google Scholar
  • For representative reviews on domino reactions, see:
  • 2a Tietze LF. Brasche G. Gericke K. Domino Reactions in Organic Synthesis   Wiley-VCH; Weinheim: 2006. 
  • 2b Nicolaou KC. Chen JS. Chem. Soc. Rev.  2009,  38:  2993 
    Search in Google Scholar
  • 2c Nicolaou KC. Edmonds DJ. Bulger PG. Angew. Chem. Int. Ed.  2006,  45:  7134 ; Angew. Chem. 2006, 118, 7292
    Search in Google Scholar
  • 2d Tietze LF. Chem. Rev.  1996,  96:  115 
    Search in Google Scholar
  • 2e Guo H.-C. Ma J.-A. Angew. Chem. Int. Ed.  2006,  45:  354 ; Angew. Chem. 2006, 118, 362
    Search in Google Scholar
  • For excellent reviews on organocatalytic domino reactions, see:
  • 3a Enders D. Grondal C. Hüttl MRM. Angew. Chem. Int. Ed.  2007,  46:  1570 ; Angew. Chem. 2007, 119, 1590
    Search in Google Scholar
  • 3b Yu X. Wang W. Org. Biomol. Chem.  2008,  6:  2037 
    Search in Google Scholar
  • 3c Jeanty M. Grondal C. Enders D. Nature Chem.  2010,  2:  167 
    Search in Google Scholar
  • 3d Poisson T. Synlett  2008,  147 
  • 3e Alba A.-N. Companyó X. Viciano M. Rios R. Curr. Org. Chem.  2009,  13:  1432 
    Search in Google Scholar
  • 4a Trost BM. Science  1991,  254:  1471 
    Search in Google Scholar
  • 4b Anastas PT. Warner JC. Green Chemistry: Theory and Practice   Oxford University Press; Oxford: 2000. 
  • 4c Newhouse T. Baran PS. Hoffmann RW. Chem. Soc. Rev.  2009,  38:  3010 
    Search in Google Scholar
  • Recent reviews:
  • 5a Palomo C. Mielgo A. Angew. Chem. Int. Ed.  2006,  45:  7876 ; Angew. Chem. 2006, 118, 8042
    Search in Google Scholar
  • 5b Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed.  2008,  47:  6138 ; Angew. Chem. 2008, 120, 6232
    Search in Google Scholar
  • 5c Erkkilä A. Majander I. Pihko PM. Chem. Rev.  2007,  107:  5416 
    Search in Google Scholar
  • 5d Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev.  2007,  107:  5471 
    Search in Google Scholar
  • 5e Pihko PM. Majander I. Erkkilä A. Top. Curr. Chem.  2009,  291:  29 
    Search in Google Scholar
  • 5f Brazier JB. Tomkinson NCO. Top. Curr. Chem.  2009,  291:  281 
    Search in Google Scholar
  • 5g Nielsen M. Worgull D. Zweifel T. Gschwend B. Bertelsen S. Jørgensen KA. Chem. Commun.  2010,  47:  632 
    Search in Google Scholar
  • Reviews on Brønsted acid catalysis:
  • 6a Akiyama T. Chem. Rev.  2007,  107:  5744 
    Search in Google Scholar
  • 6b Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
    Search in Google Scholar
  • 6c Taylor MS. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  1520 ; Angew. Chem. 2006, 118, 1550
    Search in Google Scholar
  • 6d Doyle AG. Jacobsen EN. Chem. Rev.  2007,  107:  5713 
    Search in Google Scholar
  • 6e Yamamoto H. Payette N. In Hydrogen Bonding in Organic Synthesis   Pihko PM. Wiley-VCH; Weinheim: 2009.  p.73-140  
  • 6f Kampen D. Reisinger CM. List B. Top. Curr. Chem.  2010,  291:  395 
    Search in Google Scholar
  • 6g Rueping M. Koenigs RM. Atodiresei I. Chem. Eur. J.  2010,  16:  9350 
    Search in Google Scholar
  • Selected examples from our group:
  • 7a Rueping M. Sugiono E. Azap C. Angew. Chem. Int. Ed.  2006,  45:  2617 
    Search in Google Scholar
  • 7b Rueping M. Azap C. Angew. Chem. Int. Ed.  2006,  45:  7832 
    Search in Google Scholar
  • 7c Rueping M. Sugiono E. Theissmann T. Kuenkel A. Kockritz A. Pews-Davtyan A. Nemati N. Beller M. Org. Lett.  2007,  9:  1065 
    Search in Google Scholar
  • 7d Rueping M. Sugiono E. Schoepke FR. Synlett  2007,  1441 
  • 7e Rueping M. Sugiono E. Moreth SA. Adv. Synth. Catal.  2007,  349:  759 
    Search in Google Scholar
  • 7f Rueping M. Antonchick AP. Brinkmann C. Angew. Chem. Int. Ed.  2007,  46:  6903 
    Search in Google Scholar
  • 7g Rueping M. Antonchick AP. Org. Lett.  2008,  10:  1731 
    Search in Google Scholar
  • 7h Rueping M. Antonchick AP. Angew. Chem. Int. Ed.  2008,  47:  10090 
    Search in Google Scholar
  • 7i Rueping M. Antonchick AP. Sugiono E. Grenader K. Angew. Chem. Int. Ed.  2009,  48:  908 
    Search in Google Scholar
  • 8a Michael JP. Nat. Prod. Rep.  2008,  25:  139 ; and the previous reviews in the series
    Search in Google Scholar
  • 8b Michael JP. In The Alkaloids   Vol 55:  Cordell G. Academic Press; New York: 2001.  p.91-258  
    Search in Google Scholar
  • 8c Michael JP. Beilstein J. Org. Chem.  2007,  3:  No. 27 
    Search in Google Scholar
  • Recent approaches toward the synthesis of quinolizidines and indolizidines:
  • 9a Amorde SM. Jewett IT. Martin SF. Tetrahedron  2009,  65:  3222 
    Search in Google Scholar
  • 9b Yang D. Micalizio GC. J. Am. Chem. Soc.  2009,  131:  17548 ; and the references cited therein
    Search in Google Scholar
  • 10a Rueping M. Theissmann T. Antonchick AP. Synlett  2006,  1071 
  • 10b Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  3683 ; Angew. Chem. 2006, 118, 3765
    Search in Google Scholar
  • 10c Rueping M. Theissmann T. Antonchick AP. In Catalysts for Fine Chemical Synthesis   Vol. 5:  Roberts SM. Whittall J. J. Wiley and Sons; New York: 2007.  p.170 
    Search in Google Scholar
  • 10d Rueping M. Theissmann T. Raja S. Bats JB. Adv. Synth. Catal.  2008,  350:  1001 
    Search in Google Scholar
  • 10e Rueping M. Theissmann T. Chem. Sci.  2010,  1:  473 
    Search in Google Scholar
  • 10f Rueping M. Sugiono E. Steck A. Theissmann T. Adv. Synth. Catal.  2010,  352:  281 
    Search in Google Scholar
  • 11a Rueping M. Sugiono E. Schoepke FR. Synlett  2010,  852 
  • 11b Rueping M. Azap C. Sugiono E. Theissmann T. Synlett  2005,  2367 
  • 11c Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett.  2005,  7:  3781 
    Search in Google Scholar
  • 11d Rueping M. Koenigs RM. Chem. Commun.  2011,  47:  304 
    Search in Google Scholar
  • 11e Rueping M. Brinkmann C. Antonchick AP. Atodiresei I. Org. Lett.  2010,  12:  4604 
    Search in Google Scholar
  • 11f Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  6751 
    Search in Google Scholar
  • 11g Rueping M. Tato F. Schoepke FR. Chem. Eur. J.  2010,  16:  2688 
    Search in Google Scholar
  • 11h Rueping M. Merino E. Koenigs RM. Adv. Synth. Catal.  2010,  352:  2629 
    Search in Google Scholar
  • 11i Rueping M. Antonchick AP. Angew. Chem. Int. Ed.  2007,  46:  4562 
    Search in Google Scholar
  • 11j Rueping M. Antonchick AP. Angew. Chem. Int. Ed.  2008,  47:  5836 
    Search in Google Scholar
  • 12 Adapted from: Stevens RV. Canary JW. J. Org. Chem.  1990,  55:  2237 
    CrossrefSearch in Google Scholar
  • 13 Bunce RA. Herron DM. Johnson LB. Kotturi SV. J. Org. Chem.  2001,  66:  2822 
    CrossrefSearch in Google Scholar
  • Reviews on BINOL-phosphoric acids:
  • 14a Terada M. Chem. Commun.  2008,  4097 
  • 14b Terada M. Synthesis  2010,  1929 
  • 14c Terada M. Bull. Chem. Soc. Jpn.  2010,  101 
  • 14d Zamfir A. Schenker V. Freund M. Tsogoeva SB. Org. Biomol. Chem.  2010,  8:  5262 
    Search in Google Scholar
  • Selected examples for the application of BINOL-based N-triflyl phosphoramides in catalysis:
  • 15a Nakashima D. Yamamoto H. J. Am. Chem. Soc.  2006,  128:  9626 
    Search in Google Scholar
  • 15b Jiao P. Nakashima D. Yamamoto H. Angew. Chem. Int. Ed.  2008,  47:  2411 ; Angew. Chem. 2008, 120, 2445
    Search in Google Scholar
  • 15c Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 ; Angew. Chem. 2007, 119, 2143
    Search in Google Scholar
  • 15d Rueping M. Ieawsuwan W. Adv. Synth. Catal.  2009,  351:  78 
    Search in Google Scholar
  • 15e Rueping M. Nachtsheim BJ. Moreth SA. Bolte M. Angew. Chem. Int. Ed.  2008,  47:  593 ; Angew. Chem. 2008, 120, 603
    Search in Google Scholar
  • 15f Rueping M. Theissmann T. Kuenkel A. Koenigs RM. Angew. Chem. Int. Ed.  2008,  47:  6798 ; Angew. Chem. 2008, 120, 6903
    Search in Google Scholar
  • 15g Rueping M. Lin M.-Y. Chem. Eur. J.  2010,  16:  4169 
    Search in Google Scholar
  • 15h Rueping M. Nachtsheim BJ. Koenigs RM. Ieawsuwan W. Chem. Eur. J.  2010,  16:  13116 
    Search in Google Scholar
  • 15i Zeng M. Kang Q. He Q.-L. You S.-L. Adv. Synth. Catal.  2008,  350:  2169 
    Search in Google Scholar
  • 15j Enders D. Narine A. Toulgoat F. Bisschops T. Angew. Chem. Int. Ed.  2008,  47:  5661 ; Angew. Chem. 2008, 120, 5744
    Search in Google Scholar
  • 15k Rueping M. Nachtsheim BJ. Synlett  2010,  119 
  • 16 Larson GL. Klesse R. J. Org. Chem.  1985,  50:  3627 
    Search in Google Scholar
17

Running the reaction in refluxing toluene led to decomposition.

18

Rueping, M.; Koenigs, R. M.; Borrmann, R.; Zoller, J.; Weirich, T. E.; Mayer, J. manuscript in preparation.