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)

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.

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