PDF herunterladen
Synlett 2011(3): 323-326  
DOI: 10.1055/s-0030-1259318
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Chiral Brønsted Acids and Their Calcium Salts in Catalytic Asymmetric Mannich Reactions of Cyclic 1,3-Diketones

Magnus Rueping*, Teerawut Bootwicha, Erli Sugiono
Institute of Organic Chemistry, RWTH-Aachen University, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092665; e-Mail: Magnus.Rueping@rwth-aachen.de;
Weitere Informationen

Publikationsverlauf

Received 9 July 2010
Publikationsdatum:
13. Januar 2011 (online)

   Lizenzen und Reprints Alle Artikel dieser Rubrik
Preview

Abstract

Asymmetric calcium-catalyzed direct Mannich reactions of 1,3-dicarbonyl compounds with imines have been developed. The reactions proceed under mild conditions and provide the corresponding products with high enantiomeric excess.

Key words

Mannich reaction - organocatalysis - calcium - BINOL phosphoric acid - amino acid

    References and Notes

  • For reviews on asymmetric Mannich reactions, see:
  • 1a Arend M. Westermann B. Risch N. Angew. Chem. Int. Ed.  1998,  37:  1044 
    Suche in Google Scholar
  • 1b Kobayashi S. Ishitani H. Chem. Rev.  1999,  99:  1069 
    Suche in Google Scholar
  • 1c Jarvo ER. Miller SJ. Tetrahedron  2002,  58:  2481 
    Suche in Google Scholar
  • 1d Cordova A. Acc. Chem. Res.  2004,  37:  102 
    Suche in Google Scholar
  • 1e List B. Acc. Chem. Res.  2004,  37:  548 
    Suche in Google Scholar
  • 1f Friestad GK. Mathies AK. Tetrahedron  2007,  63:  2541 
    Suche in Google Scholar
  • 1g Ting A. Schaus SE. Eur. J. Org. Chem.  2007,  5797 
  • 1h Verkade JMM. van Hemert LJC. Quaedflieg PJLM. Rutjes FPJT. Chem. Soc. Rev.  2008,  37:  29 
    Suche in Google Scholar
  • For reviews on chiral BINOL-derived phosphoric acid diesters, see:
  • 2a Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
    Suche in Google Scholar
  • 2b Akiyama T. Chem. Rev.  2007,  107:  5744 
    Suche in Google Scholar
  • 2c Kampen D. Reisinger CM. List B. Top. Curr. Chem.  2009,  291:  395 
    Suche in Google Scholar
  • 2d Terada M. Chem. Commun.  2008,  4097 
  • 2e Terada M. Bull. Chem. Soc. Jpn.  2010,  83:  101 
    Suche in Google Scholar
  • 2f Terada M. Synthesis  2010,  1929 
  • For selected examples, see:
  • 3a Storer RI. Carrera DE. Ni Y. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  84 
    Suche in Google Scholar
  • 3b Wanner MJ. van der Haas RNS. de Cuba KR. van Maarseveen JH. Hiemstra H. Angew. Chem. Int. Ed.  2007,  46:  7485 
    Suche in Google Scholar
  • 3c Rowland EB. Rowland GB. Rivera-Otero E. Antilla JC. J. Am. Chem. Soc.  2007,  129:  12084 
    Suche in Google Scholar
  • 3d Baudequin C. Zamfir A. Tsogoeva SB. Chem. Commun.  2008,  4637 
  • 3e Ackermann L. Althammer A. Synlett  2008,  995 
  • 3f Cheng X. Goddard R. Buth G. List B. Angew. Chem. Int. Ed.  2008,  47:  5079 
    Suche in Google Scholar
  • 3g Liu H. Dagousset G. Masson G. Retailleau P. Zhu J. J. Am. Chem. Soc.  2009,  131:  4598 
    Suche in Google Scholar
  • 3h Sun F.-L. Zeng M. Gu Q. You S.-L. Chem. Eur. J.  2009,  15:  8709 
    Suche in Google Scholar
  • 3i Terada M. Machioka K. Sorimachi K. Angew. Chem. Int. Ed.  2009,  48:  2553 
    Suche in Google Scholar
  • 3j Akiyama T. Katoh T. Mori K. Angew. Chem. Int. Ed.  2009,  48:  4226 
    Suche in Google Scholar
  • 3k Yue T. Wang M.-X. Wang D.-X. Masson G. Zhu J. Angew. Chem. Int. Ed.  2009,  48:  6717 
    Suche in Google Scholar
  • 3l Lu M. Zhu D. Lu Y. Zeng X. Tan B. Xu Z. Zhong G. J. Am. Chem. Soc.  2009,  131:  4562 
    Suche in Google Scholar
  • 3m Terada M. Toda Y. J. Am. Chem. Soc.  2009,  131:  6354 
    Suche in Google Scholar
  • 3n Zhang Q.-W. Fan C.-A. Zhang H.-J. Tu Y.-Q. Zhao Y.-M. Gu P. Chen Z.-M. Angew. Chem. Int. Ed.  2009,  48:  8572 
    Suche in Google Scholar
  • 3o Zeng X. Zeng X. Xu Z. Lu M. Zhong G. Org. Lett.  2009,  11:  3036 
    Suche in Google Scholar
  • 3p Müller S. List B. Angew. Chem. Int. Ed.  2009,  48:  9975 
    Suche in Google Scholar
  • 3q Ube H. Shimada N. Terada M. Angew. Chem. Int. Ed.  2010,  49:  1858 
    Suche in Google Scholar
  • 3r Lv J. Li X. Zhong L. Luo S. Cheng J.-P. Org. Lett.  2010,  12:  1096 
    Suche in Google Scholar
  • 3s Cox DJ. Smith MD. Fairbanks AJ. Org. Lett.  2010,  12:  1452 
    Suche in Google Scholar
  • 3t Bergonzini G. Gramigna L. Mazzanti A. Fochi M. Bernardi L. Ricci A. Chem. Commun.  2010,  46:  327 
    Suche in Google Scholar
  • For selected examples from our group, see:
  • 4a Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett.  2005,  7:  3781 
    Suche in Google Scholar
  • 4b Rueping M. Sugiono E. Azap C. Angew. Chem. Int. Ed.  2006,  45:  2617 
    Suche in Google Scholar
  • 4c Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 
    Suche in Google Scholar
  • 4d Rueping M. Sugiono E. Moreth SA. Adv. Synth. Catal.  2007,  349:  759 
    Suche in Google Scholar
  • 4e Rueping M. Sugiono E. Theissmann T. Kuenkel A. Köckritz A. Pews-Davtyan A. Nemati N. Beller M. Org. Lett.  2007,  9:  1065 
    Suche in Google Scholar
  • 4f Rueping M. Nachtsheim BJ. Moreth SA. Bolte M. Angew. Chem. Int. Ed.  2008,  47:  593 
    Suche in Google Scholar
  • 4g Rueping M. Antonchick AP. Org. Lett.  2008,  10:  1731 
    Suche in Google Scholar
  • 4h Rueping M. Theissmann T. Kuenkel A. Koenigs RM. Angew. Chem. Int. Ed.  2008,  47:  6798 
    Suche in Google Scholar
  • 4i Rueping M. Antonchick AP. Sugiono E. Grenader K. Angew. Chem. Int. Ed.  2009,  48:  908 
    Suche in Google Scholar
  • 4j Rueping M. Sugiono E. Steck A. Theissmann T. Adv. Synth. Catal.  2010,  352:  281 
    Suche in Google Scholar
  • 4k Rueping M. Tato F. Schoepke FR. Chem. Eur. J.  2010,  16:  2688 
    Suche in Google Scholar
  • 5a Akiyama T. Itoh J. Yokota K. Fuchibe K. Angew. Chem. Int. Ed.  2004,  43:  1566 
    Suche in Google Scholar
  • 5b Yamanaka M. Itoh J. Fuchibe K. Akiyama T. J. Am. Chem. Soc.  2007,  129:  6756 
    Suche in Google Scholar
  • 5c Itoh J. Fuchibe K. Akiyama T. Synthesis  2008,  1319 
  • 5d Akiyama T. Katoh T. Mori K. Kanno K. Synlett  2009,  1664 
  • 6a Uraguchi D. Terada M. J. Am. Chem. Soc.  2004,  126:  5356 
    Suche in Google Scholar
  • 6b Gridnev ID. Kouchi M. Sorimachi K. Terada M. Tetrahedron Lett.  2007,  48:  497 
    Suche in Google Scholar
  • 6c Terada M. Machioka K. Sorimachi K. Angew. Chem. Int. Ed.  2006,  45:  2254 
    Suche in Google Scholar
  • 6d Terada M. Machioka K. Sorimachi K.
    J. Am. Chem. Soc.  2007,  129:  10336 
    Suche in Google Scholar
  • 6e Terada M. Tanaka H. Sorimachi K. Synlett  2008,  1661 
  • 6f Hatano M. Moriyama K. Maki T. Ishihara K. Angew. Chem. Int. Ed.  2010,  49:  3823 
    Suche in Google Scholar
  • 7a Guo Q.-X. Liu H. Guo C. Luo S.-W. Gu Y. Gong L.-Z. J. Am. Chem. Soc.  2007,  129:  3790 
    Suche in Google Scholar
  • 7b Dagousset G. Drouet F. Masson G. Zhu J. Org. Lett.  2009,  11:  5546 
    Suche in Google Scholar
  • 8a Akiyama T. Honma Y. Itoh J. Fuchibe K. Adv. Synth. Catal.  2008,  350:  399 
    Suche in Google Scholar
  • 8b Sickert M. Schneider C. Angew. Chem. Int. Ed.  2008,  47:  3631 
    Suche in Google Scholar
  • 8c Giera DS. Sickert M. Schneider C. Synthesis  2009,  3797 
  • 8d Sickert M. Abels F. Lang M. Sieler J. Birkemeyer C. Schneider C. Chem. Eur. J.  2010,  16:  2806 
    Suche in Google Scholar
  • For selected recent examples of organocatalytic asymmetric direct Mannich reactions, see:
  • 9a Lou S. Taoka BM. Ting A. Schaus SE. J. Am. Chem. Soc.  2005,  127:  11256 
    Suche in Google Scholar
  • 9b Enders D. Grondal C. Vrettou M. Raabe G. Angew. Chem. Int. Ed.  2005,  44:  4079 
    Suche in Google Scholar
  • 9c Ting A. Lou S. Schaus SE. Org. Lett.  2006,  8:  2003 
    Suche in Google Scholar
  • 9d Enders D. Grondal C. Vrettou M. Synthesis  2006,  3597 
  • 9e Zhao G.-L. Córdova A. Tetrahedron Lett.  2006,  47:  7417 
    Suche in Google Scholar
  • 9f Hasegawa A. Naganawa Y. Fushimi M. Ishihara K. Yamamoto H. Org. Lett.  2006,  8:  3175 
    Suche in Google Scholar
  • 9g Tillman AL. Dixon DJ. Org. Biomol. Chem.  2007,  5:  606 
    Suche in Google Scholar
  • 9h Cheng L. Wu X. Lu Y. Org. Biomol. Chem.  2007,  5:  1018 
    Suche in Google Scholar
  • 9i Marianacci O. Micheletti G. Bernardi L. Fini F. Fochi M. Pettersen D. Sgarzani V. Ricci A. Chem. Eur. J.  2007,  13:  8338 
    Suche in Google Scholar
  • 9j Ramasastry SSV. Zhang H. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2007,  129:  288 
    Suche in Google Scholar
  • 9k Sukach VA. Golovach NM. Pirozhenko VV. Rusanov EB. Vovk MV. Tetrahedron: Asymmetry  2008,  19:  761 
    Suche in Google Scholar
  • 9l Kawanaka Y. Phillips EM. Scheidt KA.
    J. Am. Chem. Soc.  2009,  131:  18028 
    Suche in Google Scholar
  • 9m Pan Y. Zhao Y. Ma T. Yang Y. Liu H. Jiang Z. Tan C.-H. Chem. Eur. J.  2010,  16:  779 
    Suche in Google Scholar
  • 9n Ayaz M. Westermann B. Synlett  2010,  1489 
  • 10a Rueping M. Azap C. Angew. Chem. Int. Ed.  2006,  45:  7832 
    Suche in Google Scholar
  • 10b Rueping M. Sugiono E. Schoepke FR. Synlett  2007,  1441 
  • 10c Rueping M. Lin MY. Chem. Eur. J.  2010,  16:  4169 
    Suche in Google Scholar
  • For selected examples of chiral Ca(II) salts in catalysis, see:
  • 11a Suzuki T. Yamagiwa N. Matsuo Y. Sakamoto S. Yamaguchi K. Shibasaki M. Noyori R. Tetrahedron Lett.  2001,  42:  4669 
    Suche in Google Scholar
  • 11b Kumaraswamy G. Sastry MNV. Jena N. Tetrahedron Lett.  2001,  42:  8515 
    Suche in Google Scholar
  • 11c Saito S. Tsubogo T. Kobayashi S. J. Am. Chem. Soc.  2007,  129:  5364 
    Suche in Google Scholar
  • 11d Tsubogo T. Saito S. Seki K. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2008,  130:  13321 
    Suche in Google Scholar
  • 11e Kobayashi S. Tsubogo T. Saito S. Yamashita Y. Org. Lett.  2008,  10:  807 
    Suche in Google Scholar
  • 11f Poisson T. Yamashita Y. Kobayashi S. J. Am. Chem. Soc.  2010,  132:  7890 
    Suche in Google Scholar
  • 11g Poisson T. Tsubogo T. Yamashita Y. Kobayashi S. J. Org. Chem.  2010,  75:  963 
    Suche in Google Scholar
  • For our studies on chiral calcium salts in catalysis, see:
  • 12a Rueping M. Theissmann T. Kuenkel A. Koenigs RM. Angew. Chem. Int. Ed.  2008,  47:  6798 
    Suche in Google Scholar
  • 12b Rueping M. Koenigs RM. Atodiresei I. Chem. Eur. J.  2010,  16:  9350 
    Suche in Google Scholar
  • 12c Rueping M. Nachtsheim BJ. Koenigs RM. Ieawsuwan W. Chem. Eur. J.  2010,  16:  13116 
    Suche in Google Scholar
  • 13a Adair G. Mukherjee S. List B. Aldrichimica Acta  2008,  41:  31 
    Suche in Google Scholar
  • 13b Klussmann M. Ratjen L. Hoffmann S. Wakchaure V. Goddard R. List B. Synlett  2010,  2189 
14

The absolute configuration of the products was obtained from X-ray crystal structure analysis of compound 6c. On the basis of this structure the absolute configuration was assigned to be the S configuration.

15

General Procedure for Direct Mannich Reaction: In a typical experiment pyrone 2 or 1,3-cyclohexadione (5; 1.0 equiv), aldimine 3 (1.5 equiv), and the calcium catalyst (5 mol%) were suspended in Bu2O in a screw-capped vial and the resulting mixture was allowed to stir at -40 ˚C for 60-72 h. Purification of the crude product by column chromatography on silica gel afforded the corresponding product 4 or 6.
( R )- tert -Butyl(4-hydroxy-6-methyl-2-oxo-2 H -pyran-3-yl)( p -tolyl)methylcarbamate (4a): Isolated by column chromatography (CH2Cl2-acetone, 10:1) as a white solid in 49% yield and 88% ee. The ee was determined by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 90:10), flow rate: 0.6 mL/min; major enantiomer: t R = 29.59 min; minor enantiomer: t R = 22.07 min]; [α]D -6.1 (c = 1.84, CH2Cl2); mp 173-175 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 7.22 (d, J = 8.0 Hz, 2 H), 7.02 (d, J = 8.0 Hz, 2 H), 6.79 (d, J = 12.0 Hz, 1 H), 6.05 (d, J = 12.0 Hz, 1 H), 5.88 (s, 1 H), 3.41 (s, 1 H), 2.23 (s, 3 H), 2.07 (s, 3 H), 1.39 (s, 9 H). ¹³C NMR (100 MHz, CDCl3): δ = 166.10, 164.94, 161.74, 157.40, 137.67, 136.82, 129.09, 126.12, 102.60, 100.84, 81.11, 28.48, 21.05, 19.85. IR (KBr): 3359, 2980, 1700, 1651, 1530, 1161, 884, 783 cm-¹. MS (EI): m/z (%) = 345 (2) [M+], 339 (30), 251 (41), 230 (58), 200(100), 145 (64), 77 (92).
( R )- tert -Butyl(2-hydroxy-6-oxocyclohex-1-enyl)( p -tolyl)-methylcarbamate (6a): Isolated by column chromatography (CH2Cl2-acetone, 10:1) as a white solid in 47% yield and 73% ee. The ee was determined by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 92:8), flow rate: 0.6 mL/min; major enantiomer: t R = 20.23 min; minor enantiomer: t R = 17.98 min]; [α]D +4.43 (c = 0.75, CH2Cl2); mp 132-134 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 10.60 (br s, 1 H), 7.19 (d, J = 8.0 Hz, 2 H), 7.00 (d, J = 8.0 Hz, 2 H), 6.82 (d, J = 9.9 Hz, 1 H), 5.99 (d, J = 9.9 Hz, 1 H), 2.45 (t, J = 6.0 Hz, 2 H), 2.22 (s, 5 H), 1.79-1.89 (m, 2 H), 1.35 (s, 9 H). ¹³C NMR (100 MHz, CDCl3): δ = 173.73, 157.32, 136.00, 128.80, 125.92, 116.22, 80.60, 48.78, 37.02, 29.64, 28.54, 21.15, 20.62. IR (KBr): 3455, 2922, 1710, 1490, 1165, 1025, 779 cm-¹. MS (EI): m/z (%) = 331 (56) [M+], 266 (58), 239 (92), 194 (100), 116 (58), 78 (52), 70 (98).