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Synthesis 2011(16): 2540-2548  
DOI: 10.1055/s-0030-1260102
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric Synthesis of 2-Substituted Hexahydroquinolin-4-ones Using a Pd-Catalyzed Asymmetric Allylic Amination and Intramolecular Mannich Reaction: Catalytic Asymmetric Synthesis of 2-epi-cis-195A

Kazumi Kakugawa, Tetsuhiro Nemoto, Yuta Kohno, Yasumasa Hamada*
Graduate School of Pharmaceutical Sciences, Chiba University, 1-33, Yayoi-cho, Inage-ku, 263-8522, Japan
Fax: +81(43)2902987; e-Mail: hamada@p.chiba-u.ac.jp;
Further Information

Publication History

Received 12 May 2011
Publication Date:
14 July 2011 (online)

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Abstract

A novel method of the enantioselective synthesis of 2-substituted hexahydroquinolin-4-ones is described. The method relies on a Pd-catalyzed asymmetric allylic amination using a chiral diaminophosphine oxide (DIAPHOX) preligand and diastereoselective intramolecular Mannich reaction. The developed synthetic method could be applied to the catalytic asymmetric synthesis of (+)-2-epi-cis-195A.

Key word

asymmetric allylic amination - asymmetric synthesis - chiral diaminophosphine oxide - decahydroquinoline alkaloid - intramolecular Mannich reaction - palladium

    References

  • 1 Daly JW. Tokuyama T. Habermehl G. Karle IL. Witkop B. Liebigs Ann. Chem.  1969,  729:  198 
    Google Scholar
  • 2a Tokuyama T. Nishimori N. Karle IL. Edwards MW. Daly JW. Tetrahedron  1986,  42:  3453 
    Google Scholar
  • 2b Tokuyama T. Tsujita T. Shimada A. Garraffo HM. Spande TF. Daly JW. Tetrahedron  1991,  47:  5401 
    Google Scholar
  • 2c Garraffo HM. Caceres J. Daly JW. Spande TF. Andriamaharavo NR. Andriantsiferana M. J. Nat. Prod.  1993,  56:  1016 
    Google Scholar
  • 2d Daly JW. Ware N. Saporito RA. Spande TF. Garraffo HM. J. Nat. Prod.  2009,  72:  1110 
    Google Scholar
  • 3 Garraffo HM. Spande TF. Daly JW. Baldessari A. Gros EG. J. Nat. Prod.  1993,  56:  357 
    CrossrefGoogle Scholar
  • 4a Steffan B. Tetrahedron  1991,  47:  8729 
    Google Scholar
  • 4b Davis RA. Carroll AR. Quinn RJ. J. Nat. Prod.  2002,  65:  454 
    Google Scholar
  • 4c Wright AD. Goclik E. König GM. Kaminsky R.
    J. Med. Chem.  2002,  45:  3067 
    Google Scholar
  • 5 Kubanek J. Williams DE. Dilip de Silva E. Allen T. Andersen RJ. Tetrahedron Lett.  1995,  36:  6189 
    CrossrefGoogle Scholar
  • 6a Jones TH. Gorman JST. Snelling RR. Delabie JHC. Blum MS. Garraffo H. Jain P. Daly JW. Spande TF. Chem. Ecol.  1999,  25:  1179 
    Google Scholar
  • 6b Daly JW. Garraffo HM. Jain P. Spande TF. Snelling RR. Jaramillo C. Rand AS. J. Chem. Ecol.  2000,  26:  73 
    Google Scholar
  • 7a Spande TF. Jain P. Garraffo HM. Pannell LK. Yeh HJC. Daly JW. Fukumoto S. Imamura K. Tokuyama T. Torres JA. Snelling RR. Jones TH.
    J. Nat. Prod.  1999,  62:  5 
    Google Scholar
  • 7b Daly JW. Spande TF. Garraffo HM. J. Nat. Prod.  2005,  68:  1556 
    Google Scholar
  • 8a Daly JW. Nishizawa Y. Edwards MW. Waters JA. Aronstam RS. Neurochem. Res.  1991,  16:  489 
    Google Scholar
  • 8b Daly JW. Nishizawa Y. Padgett WL. Tokuyama T. McCloskey PJ. Waykole L. Aronstam RS. Neurochem. Res.  1991,  16:  1207 
    Google Scholar
  • 9 Warnick JE. Jessup PJ. Overman LE. Eldefrawi ME. Nimit Y. Daly JW. Albuquerque EX. Mol. Pharmacol.  1982,  22:  565 
    Google Scholar
  • 10a Akashi M. Sato Y. Mori M. J. Org. Chem.  2001,  66:  7873 ; and references cited therein
    Google Scholar
  • 10b Girard N. Hurvois J.-P. Moinet C. Toupet L. Eur. J. Org. Chem.  2005,  2269 
    Google Scholar
  • 10c Saeki M. Toyota M. Tetrahedron Lett.  2010,  51:  4620 
    Google Scholar
  • 11a Oppolzer W. Flaskamp E. Bieber LW. Helv. Chim. Acta  2001,  84:  141 ; and references cited therein
    Google Scholar
  • 11b Amat M. Griera R. Fabregat R. Molins E. Bosch J. Angew. Chem. Int. Ed.  2008,  47:  3348 
    Google Scholar
  • 11c Lauzon S. Tremblay F. Gagnon D. Godbout C. Chabot C. Mercier-Shanks C. Perreault S. DeSeve H. Spino C. J. Org. Chem.  2008,  73:  6239 
    Google Scholar
  • 11d Amat M. Fabregat R. Griera R. Florindo P. Molins E. Bosch J. J. Org. Chem.  2010,  75:  3797 
    Google Scholar
  • 12 Dijk EW. Panella L. Pinho P. Naasz R. Meetsma A. Minnaard AJ. Feringa BL. Tetrahedron  2004,  60:  9687 
    CrossrefGoogle Scholar
  • 13a Neidhöfer J. Blechert S. Synthesis  2004,  3047 
    Google Scholar
  • 13b Holub N. Neidhöfer J. Blechert S. Org. Lett.  2005,  7:  1227 
    Google Scholar
  • 13c Weymann M. Schultz-Kukula M. Kunz H. Tetrahedron Lett.  1998,  39:  7835 
    Google Scholar
  • 13d Fearnley SP. Thongsornkleeb C. J. Org. Chem.  2010,  75:  933 
    Google Scholar
  • 14 Comins DL. Dehghani A. J. Org. Chem.  1995,  60:  794 
    CrossrefGoogle Scholar
  • 15a Fujimoto R. Kishi Y. Tetrahedron Lett.  1981,  22:  4197 
    Google Scholar
  • See also:
  • 15b Fujimoto R. Kishi Y. Blount JF.
    J. Am. Chem. Soc.  1980,  102:  7154 
    Google Scholar
  • 15c Wei L.-L. Hsung RP. Sklenicka HM. Gerasyuto AI. Angew. Chem. Int. Ed.  2001,  40:  1516 
    Google Scholar
  • 15d Santarem M. Vanucci-Bacqué C. Lhommet G. J. Org. Chem.  2008,  73:  6466 
    Google Scholar
  • For other representative asymmetric syntheses of natural products with a bicyclic decahydroquinoline skeleton; Lepadins:
  • 16a Toyooka N. Okumura M. Takahata H.
    J. Org. Chem.  1999,  64:  2182 
    Google Scholar
  • 16b Ozawa T. Aoyagi S. Kibayashi C. Org. Lett.  2000,  2:  2955 
    Google Scholar
  • 16c Pu X. Ma D. Angew. Chem. Int. Ed.  2004,  43:  4222 
    Google Scholar
  • 16d Niethe A. Fischer D. Blechert S. J. Org. Chem.  2008,  73:  3088 
    Google Scholar
  • 16e Li G. Hsung RP. Slafer BW. Sagamanova IK. Org. Lett.  2008,  10:  4991 
    Google Scholar
  • 16f Barbe G. Charette AB. J. Am. Chem. Soc.  2008,  130:  13873 
    Google Scholar
  • Luciduline:
  • 16g Comins DL. Brooks CA. Al-awar RS. Goehring RR. Org. Lett.  1999,  1:  229 
    Google Scholar
  • Phlegmarines:
  • 16h Comins DL. Libby AH. Al-awar RS. Foti CJ. J. Org. Chem.  1999,  64:  2184 
    Google Scholar
  • 16i Wolfe BH. Libby AH. Al-awar RS. Foti CJ. Comins DL. J. Org. Chem.  2010,  75:  8564 
    Google Scholar
  • Lycoposerramines:
  • 16j Tanaka T. Kogure N. Kitajima M. Takayama H. J. Org. Chem.  2009,  74:  8675 
    Google Scholar
  • Lycoperin A:
  • 16k Nakamura Y. Burke AM. Kotani S. Ziller JW. Rychnovsky SD. Org. Lett.  2010,  12:  72 
    Google Scholar
  • For recent representative references for the stereoselective synthesis of functionalized decahydroquinolines, see:
  • 17a Comins DL. Ollinger CG. Tetrahedron Lett.  2001,  42:  4115 
    Google Scholar
  • 17b Toyooka N. Okumura M. Nemoto H.
    J. Org. Chem.  2002,  67:  6078 
    Google Scholar
  • 17c Galbo FL. Occhiato EG. Guarna A. Faggi C. J. Org. Chem.  2003,  68:  6360 
    Google Scholar
  • 17d Gravier-Pelletier C. Maton W. Bertho G. Merrer YL. Tetrahedron  2003,  59:  8721 
    Google Scholar
  • 17e Banner EJ. Stevens ED. Trudell ML. Tetrahedron Lett.  2004,  45:  4411 
    Google Scholar
  • 17f Mena M. Bonjoch J. Tetrahedron  2005,  61:  8264 
    Google Scholar
  • 17g Comins DL. Kuethe JT. Miller TM. Février FC. Brooks CA. J. Org. Chem.  2005,  70:  5221 
    Google Scholar
  • 17h Mena M. Bonjoch J. Gomez Pardo D. Cossy J. J. Org. Chem.  2006,  71:  5930 
    Google Scholar
  • 17i Diaba F. Ricou E. Bonjoch J. Org. Lett.  2007,  9:  2633 
    Google Scholar
  • 17j Rueping M. Antonchick AP. Angew. Chem. Int. Ed.  2008,  47:  5836 
    Google Scholar
  • 17k Huang J. Bergmeier SC. Tetrahedron  2008,  64:  6434 
    Google Scholar
  • 17l Amat M. Fabregat R. Griera R. Bosch J. J. Org. Chem.  2009,  74:  1794 
    Google Scholar
  • 17m Guthmann H. Conole D. Wright E. Körber K. Barker D. Brimble MA. Eur. J. Org. Chem.  2009,  1944 
    Google Scholar
  • 17n Heitbaum M. Fröhlich R. Glorius F. Adv. Synth. Catal.  2010,  352:  357 
    Google Scholar
  • 17o Sethofer SG. Mayer T. Toste FD. J. Am. Chem. Soc.  2010,  132:  8276 
    Google Scholar
  • 18 Nemoto T. Matsumoto T. Masuda T. Hitomi T. Hatano K. Hamada Y. J. Am. Chem. Soc.  2004,  126:  3690 
    CrossrefPubMedGoogle Scholar
  • For reviews on DIAPHOX preligands in asymmetric transition-metal catalysis, see:
  • 19a Nemoto T. Chem. Pharm. Bull.  2008,  56:  1213 
    Google Scholar
  • 19b Nemoto T. Hamada Y. Tetrahedron  2011,  67:  667 
    Google Scholar
  • 20a Nemoto T. Masuda T. Akimoto Y. Fukuyama T. Hamada Y. Org. Lett.  2005,  7:  4447 
    Google Scholar
  • 20b Nemoto T. Fukuyama T. Yamamoto E. Tamura S. Fukuda T. Matsumoto T. Akimoto Y. Hamada Y. Org. Lett.  2007,  9:  927 
    Google Scholar
  • 20c Nemoto T. Tamura S. Sakamoto T. Hamada Y. Tetrahedron: Asymmetry  2008,  19:  1751 
    Google Scholar
  • 20d Nemoto T. Yamamoto E. Franzén R. Fukuyama T. Wu R. Fukamachi T. Kobayashi H. Hamada Y. Org. Lett.  2010,  12:  872 
    Google Scholar
  • The M06-2X functional has been found to be reliable for weak dispersion interactions such as hydrogen-bonding interaction. The molecular energy calculation using B3LYP/6-31G** indicated that 4b is 2.12 kcal/mol more stable than 4a. For the related references, see:
  • 21a Zhao Y. Truhlar DG. Acc. Chem. Res.  2008,  41:  157 
    Google Scholar
  • 21b Um JM. Gutierrez O. Schoenebeck F. Houk KN. MacMillan DWC.
    J. Am. Chem. Soc.  2010,  132:  6001 
    Google Scholar
  • 24 Comins DL. Dehghani A. Foti CJ. Joseph SP. Org. Synth.  1997,  74:  77 
    CrossrefGoogle Scholar
  • 25 Hoffmann RW. Chem. Rev.  1989,  89:  1841 
    CrossrefGoogle Scholar
  • 26 Graff M. Al Dilaimi A. Seguineau P. Rambaud M. Villieras J. Tetrahedron Lett.  1986,  27:  1577 
    CrossrefGoogle Scholar
22

See Supporting Information for details.

23

The enantiomeric excess was determined by chiral HPLC analysis.