One-Pot Reductive N-Alkylation
with Carbonyl Compounds To Give Tertiary Amines via Borane Reduction
of Imines

Masashi Tokizane; Kaori Sato; Yuki Sakami; Yoichiro Imori; Chika Matsuo; Tetsuo Ohta; Yoshihiko Ito

doi:10.1055/s-0029-1217076

PAPER

One-Pot Reductive N-Alkylation with Carbonyl Compounds To Give Tertiary Amines via Borane Reduction of Imines

Masashi Tokizane^a, Kaori Sato^a, Yuki Sakami^a, Yoichiro Imori^a, Chika Matsuo^a, Tetsuo Ohta*^b, Yoshihiko Ito^a
^a Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Kyotanabe, Kyoto 610-0394, Japan
^b Department of Biomedical Information, Faculty of Life and Medical Sciences, Doshisha University, Kyotanabe, Kyoto 610-0394, Japan
Fax: +81(774)656789; e-Mail: tota@mail.doshisha.ac.jp;

Abstract

Alle Artikel dieser Rubrik

Abstract

One-pot synthesis of tertiary amines via borane-mediated reduction of imines and reductive N-alkylation with carbonyl compounds is described. This protocol’s reducing agent is only borane in the reduction of imines, and additional reductant is not necessary in reductive N-alkylation step. When using more than two equivalents of aldehydes, reductive N-alkylation proceeded in good yield.

Key words

reductive N-alkylation - borane reduction - imines - tertiary amines - one-pot reaction

Volltext

Referenzen

References

1a Hutchins RO. Hutchins MK. In Comprehensive Organic Synthesis Vol. 8: Trost BM. Pergamon; Oxford: 1991. p.25

1b Kato H. Shibata I. Yasaka Y. Tsunoi S. Yasuda M. Baba A. Chem. Commun. 2006, 4189

1c Lee O.-Y. Law K.-L. Yang D. Org. Lett. 2009, 11: 3302

2a Rylander PN. In Hydrogenation Methods Academic Press; London: 1985. p.82

2b Imao D. Fujihara S. Yamamoto T. Ohta T. Ito Y. Tetrahedron 2005, 61: 6988

2c Xing L. Cheng C. Zhu R. Zhang B. Wang X. Hu Y. Tetrahedron 2008, 64: 11783

3 Borch RF. Bernstein MD. Durst HD. J. Am. Chem. Soc. 1971, 93: 2897

4a Abdel-Magid AF. Carson KG. Harris BD. Maryanoff CA. Shah RD. J. Org. Chem. 1996, 61: 3849

4b Matos K. Pichlmair S. Burkhardt ER. Chim. Oggi/Chem. Today 2007, 25: 17

5a Miriyala B. Bhattacharyya S. Williamson JS. Tetrahedron 2004, 60: 1463

5b Cho BT. Kang SK. Tetrahedron 2005, 61: 5725

6a Billman JH. McDowell JW. J. Org. Chem. 1961, 26: 1437

6b Trapani G. Reho A. Latrofa A. Synthesis 1983, 1013

6c Pelter A. Rosser RM. Mills S. J. Chem. Soc., Perkin Trans. 1 1984, 717

6d Bomann MD. Guch IC. DiMare M. J. Org. Chem. 1995, 60: 5995

6e Johansson A. Lindstedt E.-L. Olsson T. Acta Chem. Scand. 1997, 51: 351

6f Peterson MA. Bowman A. Morgan S. Synth. Commun. 2002, 32: 443

6g Sato S. Sakamoto T. Miyazawa E. Kikugawa Y. Tetrahedron 2004, 60: 7899

7 Suginome M. Tanaka Y. Hasui T. Synlett 2006, 1047

8 Miura K. Ootsuka K. Suda S. Nishikori H. Hosomi A. Synlett 2001, 1617

9 We attempted to detect aminoborane 2a (2; R^¹ = Ph, R^² = Bn in Scheme 2) by ^¹¹B NMR spectroscopy of the reaction mixture of imine 1a and BH₃˙SMe₂ in toluene-d ₈. We obtained a complex mixture including 2a (^¹¹B NMR: δ = 39.1 ppm), see: Maringgele W. Noltemeyer M. Teichgräber J. Meller A. Main Group Met. Chem. 2000, 23: 735 . Because of the detected existence of aminoboranes 2, these species could probably be related to the present reaction

10 Perrin DD. Armarego WLF. Purification of Laboratory Chemicals 3rd ed.: Pergamon; Oxford: 1988.

11 Taguchi K. Westheimer FH. J. Org. Chem. 1971, 36: 1570

12 Barbe G. Charette AB. J. Am. Chem. Soc. 2008, 130: 18

13 Fujita K. Enoki Y. Yamaguchi R. Tetrahedron 2008, 64: 1943

14 Shimazaki Y. Nogami T. Tani F. Odani A. Yamauchi O. Angew. Chem. Int. Ed. 2001, 40: 3859

15 de Meijere A. Williams CM. Kourdioukov A. Sviridov SV. Chaplinski V. Kordes M. Savchenko AI. Stratmann C. Noltemeyer M. Chem. Eur. J. 2002, 8: 3789

16 Shi M. Shen Y.-M. Helv. Chim. Acta 2001, 84: 3357

17 Zhang M. Flynn DL. Hanson PR. J. Org. Chem. 2007, 72: 3194

18 Ratcliff MA. Kochi JK. Tetrahedron 1972, 28: 4467

19 Brown AR. Rees DC. Rankovic Z. Morphy JR. J. Am. Chem. Soc. 1997, 119: 3288