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Synlett 2009(19): 3065-3081  
DOI: 10.1055/s-0029-1218302
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Camphor Derivatives in Asymmetric Cycloadditions and Rearrangements

Yves Langlois*, Cyrille Kouklovsky*
Laboratoire de Chimie des Procédés et des Substances Naturelles, UMR 8182, ICMMO, Université de Paris Sud, 91405 Orsay, France
e-Mail: langlois@icmo.u-psud.fr; e-Mail: cykouklo@icmo.u-psud.fr;
Further Information

Publication History

Received 25 May 2009
Publication Date:
21 October 2009 (online)

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Abstract

Camphor-derived α,β-unsaturated oxazolines and oxazoline N-oxides are, respectively, useful dienophiles and dipolarophiles in [2+4] and [2+3] diastereoselective cycloadditions. The scope and limitations of these two reactions as well as their synthetic applications in the synthesis of various natural products are discussed. The Account also covers σ-[2,3] rearrangement of oxazoline N-oxide, which gives a new insight into the mechanism of this type of reaction. Finally, recent developments in Diels-Alder organocatalyzed cycloaddition with camphor-derived sulfonylhydrazines are also discussed.

1 Introduction

2 Diels-Alder Cycloadditions

2.1 Camphor-Derived α,β-Unsaturated Oxazolines in Diels-­Alder Cycloadditions

2.2 Diels-Alder Cycloaddition with 2-Azadienes

2.3 Diels-Alder Cycloaddition with a Captodative α,β-Unsaturated Oxazoline

2.4 Approaches to the Oxahydrindane Subunit of Avermectins

3 [3+2] Cycloadditions

3.1 Camphor-Derived Oxazoline N-Oxides in [3+2] Cycloadditions

3.2 Synthetic Applications of Asymmetric [3+2] Cycloadditions with Oxazoline N-Oxides

4 Stereoselective Hetero-Claisen Rearrangement of Camphor-Derived Oxazoline N-Oxides

5 Camphor-Derived Sulfonylhydrazines as Catalysts for ­Diels-Alder Cycloadditions

6 Conclusion

Key words

cycloadditions - Diels-Alder reactions - chiral auxiliaries - rearrangements - asymmetric catalysis

    References

  • 1 For a convenient, inexpensive preparation of (-)-camphor from (-)-borneol, see: Stevens RV. Chapman KT. Weller HN. J. Org. Chem.  1980,  45:  2030 
    CrossrefGoogle Scholar
  • For the use of camphor derivatives in asymmetric synthesis, see:
  • 2a Oppolzer W. Tetrahedron  1987,  43:  1969 
    Google Scholar
  • 2b Polywka MEC. Chim. Oggi  1992,  10:  33 
    Google Scholar
  • 3 For a review concerning iminium catalysis, see: Erkkila A. Majander I. Pikho PM. Chem. Rev.  2007,  107:  5416 
    CrossrefPubMedGoogle Scholar
  • 4 Pouilhès A. Kouklovsky C. Langlois N. Langlois Y. Tetrahedron Lett.  1987,  28:  6183 
    CrossrefGoogle Scholar
  • 5 For a recent review on enantioselective Diels-Alder reactions, see: Corey EJ. Angew. Chem. Int. Ed.  2009,  48:  2100 ; and references cited therein
    CrossrefPubMedGoogle Scholar
  • 6 Daniel A. Pavia AA. Bull. Soc. Chim. Fr.  1971,  1060 
    Google Scholar
  • 8 Pouilhès A. Uriarte E. Kouklovsky C. Langlois N. Langlois Y. Tetrahedron Lett.  1989,  30:  1395 
    CrossrefGoogle Scholar
  • 10 Kouklovsky C. Pouilhès A. Langlois Y. J. Am. Chem. Soc.  1990,  112:  6672 
    CrossrefGoogle Scholar
  • 12 Alvarez C. Barkaoui L. Goasdoue N. Datran JC. Platzer N. Rudler H. Vaissermann J. J. Chem. Soc., Chem. Commun.  1989,  1507 
    CrossrefGoogle Scholar
  • For a recent review concerning the preparation of amino alcohol 36, see:
  • 13a White JD. Wardrop DJ. Sundermann KF. Org. Synth.  2002,  79 
    Google Scholar
  • See also:
  • 13b Cheng G.-I. Shei C.-T. Sung K. Chirality  2007,  19:  235 
    Google Scholar
  • 14a Pouilhès A. Langlois Y. Nshimyumukiza P. Mbiya K. Ghosez L. Bull. Soc. Chim. Fr.  1993,  130:  304 
    Google Scholar
  • 14b

    Low diastereoselectivities were observed for cyclo-additions between oxazoline 13 and cyclopentadiene with TBSOTf, TMSOTf, and Tf2O.

  • 15 Langlois Y. Pouilhès A. Tetrahedron: Asymmetry  1991,  12:  1223 
    Google Scholar
  • 17 Gassman PG. Schenck NN. J. Org. Chem.  1977,  42:  5041 
    Google Scholar
  • 18 For a review concerning avermectin synthesis, see: Blizzard TA. Org. Prep. Proced. Int.  1994,  26:  617 
    CrossrefGoogle Scholar
  • 19a Bac NV. Langlois Y. Tetrahedron Lett.  1988,  29:  2819 
    Google Scholar
  • 19b Langlois Y. Bac NV. Synlett  1991,  523 
    Google Scholar
  • 20 Morelli J.-F. Pouilhès A. Langlois Y. Tetrahedron  1997,  53:  5195 
    CrossrefGoogle Scholar
  • 21a Ashburn SP. Coates RM. J. Org. Chem.  1984,  49:  3121 
    Google Scholar
  • 21b Ashburn SP. Coates RM. J. Org. Chem.  1985,  50:  3076 
    Google Scholar
  • For [3+2] cycloadditions of camphor-derived nitrones, see:
  • 22a Ali SA. Iman NZN. Tetrahedron  2007,  63:  9134 
    Google Scholar
  • 22b Wang P.-F. Gao P. Xu P.-F. Synlett  2006,  1095 
    Google Scholar
  • 23 Baldwin SW. McFayden RB. Aubé J. Wilson JD. Tetrahedron Lett.  1991,  32:  4431 
    CrossrefGoogle Scholar
  • 24 Unpublished results from our laboratory
  • 25 Berranger T. Langlois Y. J. Org. Chem.  1995,  60:  1726 
    Google Scholar
  • 26 Kouklovsky C. Dirat O. Berranger T. Langlois Y. Tran-Huu-Dau ME. Riche C. J. Org. Chem.  1998,  63:  5123 
    CrossrefGoogle Scholar
  • 27 Collon S. Kouklovsky C. Langlois Y. Eur. J. Org. Chem.  2002,  3566 
    CrossrefGoogle Scholar
  • 28 Dirat O. Kouklovsky C. Langlois Y. Lesot P. Courtieu J. Tetrahedron: Asymmetry  1999,  10:  3197 
    CrossrefGoogle Scholar
  • For a review, see:
  • 29a See also: Cardona F. Goti A. Brandi A. Eur. J. Org. Chem.  2001,  2999 
    Google Scholar
  • 29b Stecko S. Paśniczek K. Jurczak M. Urbańczyk-Lipkowska Z. Chmielewski M. Tetrahedron: Asymmetry  2007,  18:  1085 
    Google Scholar
  • 30 Voituriez A. Moulinas J. Kouklovsky C. Langlois Y. Synthesis  2003,  1419 
    Article in Thieme ConnectGoogle Scholar
  • 31 For a related discussion, see: Iwamoto O. Shinohara R. Nagasawa K. Chem. Asian J.  2009,  4:  277 
    CrossrefGoogle Scholar
  • 32 LeBel NA. Spurlock LA. J. Org. Chem.  1964,  29:  1337 
    CrossrefGoogle Scholar
  • 33 For an earlier review, see: Dirat O. Kouklovsky C. Mauduit M. Langlois Y. Pure Appl. Chem.  2000,  72:  1721 
    CrossrefGoogle Scholar
  • 34 For a synthesis of 1233-A, see: Bates RW. Fernandez-Megia E. Ley SV. Ruck-Braun K. Tilbrook DMG. J. Chem. Soc., Perkin Trans. 1  1999,  1917 ; and references cited therein
    CrossrefGoogle Scholar
  • 35 Dirat O. Kouklovsky C. Langlois Y. J. Org. Chem.  1998,  63:  6634 
    CrossrefGoogle Scholar
  • 36 For a synthesis of tetrahydrolipstatin, see: Ghosh AK. Shurrush K. Kulkarni S. J. Org. Chem.  2009,  74:  4508 ; and references cited therein
    CrossrefGoogle Scholar
  • 37 Dirat O. Kouklovsky C. Langlois Y. Org. Lett.  1999,  1:  753 
    CrossrefGoogle Scholar
  • 38 For a synthesis of frontalin, see: Ortiz B. Sánchez-Obregón R. Toscano RA. Yuste F. Synthesis  2008,  2105 ; and references cited therein
    Article in Thieme ConnectGoogle Scholar
  • 39 Thrinh MC. Florent JC. Monneret C. Tetrahedron  1988,  44:  6633 
    CrossrefGoogle Scholar
  • 40 For a review, see: Fisher JF. Meroueh SO. Mobashery S. Chem. Rev.  2005,  105:  395 
    CrossrefGoogle Scholar
  • 41 Mauduit M. Kouklovsky C. Langlois Y. Eur. J. Org. Chem.  2000,  1595 
    CrossrefGoogle Scholar
  • 42a Blaise EE. C. R. Acad. Sci.  1901,  132:  478 
    Google Scholar
  • For a recent review, see:
  • 42b Rao HSP. Rafi S. Padmavathy K. Tetrahedron  2008,  64:  9037 
    Google Scholar
  • 43 Mauduit M. Kouklovsky C. Langlois Y. Riche C. Org. Lett.  2000,  2:  1053 
    CrossrefGoogle Scholar
  • 44 Mauduit M. Kouklovsky C. Langlois Y. Tetrahedron Lett.  1998,  39:  6857 
    CrossrefGoogle Scholar
  • 45 For syntheses of carbocyclic nucleosides, see: Jeong LS. Lee JA. Antiviral Chem. Chemother.  2004,  15:  235 ; and references cited therein
    Google Scholar
  • 46 McGill JM. Synthesis  1993,  1089 
    Article in Thieme ConnectGoogle Scholar
  • 47 Berranger T. Langlois Y. Tetrahedron Lett.  1995,  36:  5523 
    Google Scholar
  • 48 For a review on radical denitration, see: Ono N. Kaji A. Synthesis  1986,  693 
    Article in Thieme ConnectGoogle Scholar
  • 49 Denmark SE. Senanayake CBW. J. Org. Chem.  1993,  58:  1853 
    CrossrefGoogle Scholar
  • 50 Bedel D. Urban D. Langlois Y. Tetrahedron Lett.  2002,  43:  607 
    CrossrefGoogle Scholar
  • 51 Cummins CH. Coates RM. J. Org. Chem.  1983,  48:  2070 
    CrossrefGoogle Scholar
  • 52 Abramovitch DA. Abramovitch RA. Benecke H. Heterocycles  1985,  23:  25 
    CrossrefGoogle Scholar
  • 53 Dalko PI. Langlois Y. Tetrahedron Lett.  1998,  39:  2107 
    CrossrefGoogle Scholar
  • 54a Ahrendt KA. Borths CJ. MacMillan DWC. J. Am. Chem. Soc.  2000,  122:  4243 
    Google Scholar
  • See also:
  • 54b Gordillo R. Houk KN. J. Am. Chem. Soc.  2006,  128:  3543 
    Google Scholar
  • 55 For organocatalyzed Diels-Alder cycloadditions, see: Hayashi Y. Samanta S. Gotoh H. Ishikawa H. Angew. Chem. Int. Ed.  2008,  47:  6634 ; and references cited therein
    CrossrefGoogle Scholar
  • 56 During the completion of this work, the use of camphoric acid hydrazides as catalysts in Diels-Alder cycloaddition was reported; see: Lemay M. Aumand L. Ogilvie WW. Adv. Synth. Catal.  2007,  349:  441 ; and references cited therein
    CrossrefGoogle Scholar
  • 57 Almost the same study was reported before the publication of our own work: He H. Pei B.-J. Chou H.-H. Tian T. Lee AWM. Org. Lett.  2008,  10:  2421 
    CrossrefGoogle Scholar
  • 58 Langlois Y. Petit A. Rémy P. Scherrmann M.-C. Kouklovsky C. Tetrahedron Lett.  2008,  49:  5576 
    CrossrefGoogle Scholar
  • 59 For a recent use of camphor-derived sulfonylhydrazines in an aza-Michael addition, see: Chen L.-Y. He H. Pei B.-J. Chan W.-H. Lee AWM. Synthesis  2009,  1573 
    Article in Thieme ConnectGoogle Scholar
  • For a similar observation, see:
  • 60a Desimoni G. Faita G. Mella M. Piccini F. Toscanini M. Eur. J. Org. Chem.  2007,  1529 
    Google Scholar
  • 60b Desimoni G. Faita G. Mella M. Toscanini M. Boiocchi M. Chem. Eur. J.  2007,  13:  9478 
    Google Scholar
7

Trifluoromethanesulfonic anhydride, even freshly distilled, promoted at -78 ˚C the polymerization of cyclopentadiene; however, the use of methyloxirane as proton scavenger precluded this polymerization. See ref. 14.

9

Danishefsky’s diene was not stable in the presence of trifluoroacetic anhydride.

11

All product diastereomer analyses were carried out by capillary chromatography coupled with mass spectrometric analysis or by HPLC. The four diastereomers corresponding to the adduct 21 were prepared as a sample for comparison.

16

Cycloadduct 54 was prepared independently by thiophenyl-ation of adduct 26 of known configuration. The configura-tions at C2 in adducts 55, 56, and 57 were deduced after NMR experiments.