PDF herunterladen
Synlett 2011(9): 1251-1254  
DOI: 10.1055/s-0030-1260539
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Brønsted Acid Catalyzed Reductive Amination with Benzothiazoline as a Highly Efficient Hydrogen Donor

Chen Zhu, Takahiko Akiyama*
Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan
Fax: +81(3)59921029; e-Mail: takahiko.akiyama@gakushuin.ac.jp;
Weitere Informationen

Publikationsverlauf

Received 7 February 2011
Publikationsdatum:
20. April 2011 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Reductive amination of aldehyde and amine proceeded smoothly in the presence of benzothiazoline as efficient hydrogen source by means of 20 mol% trifluoroacetic acid to give the corresponding amines in excellent yields. Hydrogen-donor abilities of benzothiazoline, benzimidazoline, and benzoxazoline were compared.

Key words

reduction - reductive amination - benzothiazoline - transfer hydrogenation - phosphoric acid

    References and Notes

  • For general reviews of metal-catalyzed asymmetric reductive amination, see:
  • 1a Ohkuma T. Noyori R. In Comprehensive Asymmetric Catalysis   Suppl. 1:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; New York: 2004. 
    Google Scholar
  • 1b Gomez S. Peters JA. Maschmeyer T. Adv. Synth. Catal.  2002,  344:  1037 
    Google Scholar
  • 1c Tararov VI. Börner A. Synlett  2005,  203 
    Google Scholar
  • For asymmetric synthesis, see:
  • 2a Blaser H.-U. Buser H.-P. Jalett H.-P. Pugin B. Spindler F. Synlett  1999,  867 
    Google Scholar
  • 2b Kadyrov R. Riermeier TH. Angew. Chem. Int. Ed.  2003,  42:  5472 
    Google Scholar
  • 2c Li C. Villa-Marcos B. Xiao J. J. Am. Chem. Soc.  2009,  131:  6967 
    Google Scholar
  • 2d Steinhuebel D. Sun Y. Matsumura K. Sayo N. Saito T. J. Am. Chem. Soc.  2009,  131:  11316 
    Google Scholar
  • 2e Steinhuebel D. Sun Y. Matsumura K. Sayo N. Saito T. J. Am. Chem. Soc.  2009,  131:  11316 
    Google Scholar
  • For biocatalysis, see:
  • 2f Koszelewski D. Lavandera I. Clay D. Guebitz GM. Rozzell D. Kroutil W. Angew. Chem. Int. Ed.  2008,  47:  9337 
    Google Scholar
  • For achiral reactions, see:
  • 3a Chandrasekhar S. Reddy CR. Ahmed M. Synlett  2000,  1655 
    Google Scholar
  • 3b Apodaca R. Xiao W. Org. Lett.  2001,  3:  1745 
    Google Scholar
  • 3c Gross T. Seayad AM. Ahmad M. Beller M. Org. Lett.  2002,  4:  2055 
    Google Scholar
  • 4 Eisner U. Kuthan J. Chem. Rev.  1972,  72:  1 
    CrossrefGoogle Scholar
  • For representative reviews on Hantzsch esters, see:
  • 5a Ouellet SG. Walji AM. MacMillan DWC. Acc. Chem. Res.  2007,  40:  1327 
    Google Scholar
  • 5b You S.-L. Chem. Asian J.  2007,  2:  820 
    Google Scholar
  • 5c Connon SJ. Org. Biomol. Chem.  2007,  5:  3407 
    Google Scholar
  • 5d Rueping M. Sugiono E. Schoepke FR. Synlett  2010,  852 
    Google Scholar
  • 6a Steevens JB. Pandit UK. Tetrahedron  1983,  39:  1395 
    Google Scholar
  • 6b Fujii M. Aida T. Yoshihara M. Ohno A. Bull. Chem. Soc. Jpn.  1989,  62:  3845 
    Google Scholar
  • 6c Itoh T. Nagata K. Kurihara A. Miyazaki M. Ohsawa A. Tetrahedron Lett.  2002,  43:  3105 
    Google Scholar
  • See also:
  • 6d Che J. Lam Y. Synlett  2010,  2415 
    Google Scholar
  • 7a Menche D. Arikan F. Synlett  2006,  841 
    Google Scholar
  • 7b Zhang Z. Schreiner PR. Synlett  2007,  1455 
    Google Scholar
  • 7c Rueping M. Azap C. Sugiono E. Theissmann T. Synlett  2005,  2367 
    Google Scholar
  • 7d Wakchaure VN. Nicoletti M. Ratjen L. List B. Synlett  2010,  2708 
    Google Scholar
  • See also:
  • 7e Menche D. Hassfeld J. Li J. Menche G. Ritter A. Rudolph S. Org. Lett.  2006,  8:  741 
    Google Scholar
  • 8a Storer RI. Carrera DE. Ni Y. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  84 
    Google Scholar
  • 8b Hoffmann S. Nicoletti M. List B. J. Am Chem. Soc.  2006,  128:  13074 
    Google Scholar
  • 8c Wakchaure VN. Zhou J. Hoffmann S. List B. Angew. Chem. Int. Ed.  2010,  49:  4612 
    Google Scholar
  • For reviews on chiral Brønsted acid catalysis, see:
  • 9a Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
    Google Scholar
  • 9b Akiyama T. Chem. Rev.  2007,  107:  5744 
    Google Scholar
  • 9c Connon SJ. Angew. Chem. Int. Ed.  2006,  45:  3909 
    Google Scholar
  • 9d Terada M. Chem. Commun.  2008,  4097 
    Google Scholar
  • 9e Terada M. Synthesis  2010,  1929 
    Google Scholar
  • 9f Zamfir A. Schenker S. Freund M. Tsogoeva SB. Org. Biomol. Chem.  2010,  8:  5262 
    Google Scholar
  • For reduction of imines, see:
  • 10a Hoffmann S. Seayad AM. List B. Angew. Chem. Int. Ed.  2005,  44:  7424 
    Google Scholar
  • 10b Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett.  2005,  7:  3781 
    Google Scholar
  • 10c Li GL. Liang YX. Antilla JC. J. Am. Chem. Soc.  2007,  129:  5830 
    Google Scholar
  • 10d Kang Q. Zhao ZA. You SL. Adv. Synth. Catal.  2007,  349:  1657 ; Corrigendum: Adv. Synth. Catal. 2007, 349, 2075
    Google Scholar
  • 10e Kang Q. Zhao ZA. You SL. Org. Lett.  2008,  10:  2031 
    Google Scholar
  • 10f Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  3683 
    Google Scholar
  • 10g Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed.  2006,  45:  6751 
    Google Scholar
  • 10h Rueping M. Merino E. Koenigs RM. Adv. Synth. Catal.  2010,  352:  2629 
    Google Scholar
  • See also:
  • 10i Li G. Antilla JC. Org. Lett.  2009,  11:  1075 
    Google Scholar
  • 10j Han Z.-Y. Xiao H. Chen X.-H. Gong L.-Z. J. Am. Chem. Soc.  2009,  131:  9182 
    Google Scholar
  • 10k Liu X.-Y. Che C.-M. Org. Lett.  2009,  11:  4204 
    Google Scholar
  • For reduction by menas of iminium catalysis, see:
  • 11a Ouellet SG. Tuttle JB. MacMillan DWC. J. Am. Chem. Soc.  2005,  127:  32 
    Google Scholar
  • 11b Tuttle JB. Ouellet SG. MacMillan DWC. J. Am. Chem. Soc.  2006,  128:  12662 
    Google Scholar
  • 12 For the study on the hydride donor ability, see: Richter D. Mayr H. Angew. Chem. Int. Ed.  2009,  48:  1958 
    CrossrefPubMedGoogle Scholar
  • 13 Davies PR, and Askew HF. inventors; US  4708810. 
  • 14a Chikashita H. Miyazaki M. Itoh K. Synthesis  1984,  308 
    Google Scholar
  • 14b Chikashita H. Miyazaki M. Itoh K. J. Chem. Soc., Perkin Trans. 1  1987,  699 
    Google Scholar
  • For chiral Brønsted acid catalyzed enantioselective transfer hydrogenation of imines employing benzothiazoline as a hydrogen donor, see:
  • 15a Zhu C. Akiyama T. Org. Lett.  2009,  11:  4180 
    Google Scholar
  • 15b Zhu C. Akiyama T. Adv. Synth. Catal.  2010,  352:  1846 
    Google Scholar
  • See also:
  • 15c Enders D. Liebich JX. Raabe G. Chem. Eur. J.  2010,  16:  9763 
    Google Scholar
16

Aliphatic amines such as benzylamine and n-pentylamine did not give the reduction products.

17

The reactions were performed with 20 mol% TFA in CH2Cl2 at 0.07 M concentration.