A General One-Pot, Three-Component Mono N-Alkylation of Amines and Amine Derivatives in Lithium Perchlorate/Diethyl Ether Solution

Akbar Heydari; Hossein Tavakol; Saied Aslanzadeh; Jamshid Azarnia; Nafiseh Ahmadi

doi:10.1055/s-2005-861798

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A General One-Pot, Three-Component Mono N-Alkylation of Amines and Amine Derivatives in Lithium Perchlorate/Diethyl Ether Solution

Akbar Heydari*, Hossein Tavakol, Saied Aslanzadeh, Jamshid Azarnia, Nafiseh Ahmadi
Chemistry Department, Tarbiat Modarres University, P. O. Box 14155-4838, Tehran, Iran
Fax: +98(21)8006544; e-Mail: akbar.heydari@gmx.de;

Abstract

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Abstract

An efficient, general procedure for reductive monoalkylation of amines and amine derivatives with aldehydes is reported. Treatment of aldehydes with primary amines, secondary amines, O-trimethylsilylhydroxylamine, and N,N-dimethylhydrazine in lithium perchlorate/diethyl ether and trimethylsilyl chloride, followed by BH₃·NEt₃ reduction, and straightforward workup afforded secondary amines, tertiary amines, N-substituted hydroxylamines, and hydrazines, respectively. Reductive alkylation of α-amino esters with aldehydes afforded the corresponding N-monoalkylated α-amino esters selectively.

Key words

lithium perchlorate - reductive amination - alkylation - amines

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References

1a Tietze LF. Chem. Rev. 1996, 96: 115

1b Bienayme H. Hulme C. Oddon G. Schmitt P. Chem. Eur. J. 2000, 6: 321

1c Doemling A. Ugi I. Angew. Chem. Int. Ed. 2000, 39: 3168

2 Mannich C. Kroesche W. Arch. Pharm. Ber. Dtsch. Pharm. Ges. 1912, 250: 647

3 Kleinman EF. In Comprehensive Organic Synthesis Vol. 2: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.893

4 Ishimaru K. Kojima T. Tetrahedron Lett. 2003, 44: 5441

5 Arend M. Westermann B. Rish N. Angew. Chem. Int. Ed. 1998, 37: 1044

6a Seebach D. Schiess M. Schweizer WB. Chimia 1985, 39: 272

6b Schiess M. Ph.D. Dissertation Eidgenoessische Technische Hochschule; Zürich: 1986.

6c The corresponding author of this paper discovered the first example of α-aminoalkylation of aldehydes using 5.0 M LiClO₄/Et₂O solution as a reaction medium: Heydari A. PhD Dissertation University of Giessen; Giessen: 1994.

6d A partial account of this discovery was reported: Saidi MR. Heydari A. Ipaktschi J. Chem Ber. 1994, 127: 1761

6e In comparison to the classical Mannich conditions, these one-pot three-component reactions need lower reaction temperatures and much shorter reaction times. In this way, many undesired side reactions, which often cause problems in the Mannich reaction, are avoided. One can therefore also successfully use reagents (e. g. enolate), which are normally impossible under the classical Mannich conditions. It is also possible to carry out the reaction with high degrees of regio- and stereoselectivity. The most important one-pot three-component of Mannich-type reaction in LPDE solution is described briefly in: Heydari A. Tetrahedron 2002, 58: 6777

7a Katritzky AR. Fan W.-Q. Long Q.-H. Synthesis 1993, 229

7b Kobayashi S. Ishitani H. Komiyama S. Oniciu DC. Katritzky AR. Tetrahedron Lett. 1996, 37: 3731

8a Baxter EW. Reitz AB. Org. React. 2002, 59: 1

8b Whitesell JK. In Comprehensive Organic Synthesis Vol. 6: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.25

9a Smith MB. March J. Advanced Organic Chemistry Wiley; New York: 2001. p.1187

9b Abdel-Majid AF. Carson KG. Harris BD. Maryanoff CA. Shah RD. J. Org. Chem. 1996, 61: 3849

10 Miriyala B. Bhattacharyya S. Williamson JS. Tetrahedron 2004, 60: 1463 ; and references cited therein

11 Heydari A. Mehrdad M. Tavakol H. Synthesis 2003, 1962

12 Sakai N. Hirasawa M. Hamajima T. Konakahara T. J. Org. Chem. 2003, 68: 483 ; and references cited therein

13 Gante J. Synthesis 1989, 405

14 Ragnarsson U. Chem. Soc. Rev. 2001, 30: 205

15 Kobayashi S. Ishitani H. Chem. Rev. 1999, 99: 1069

16a Brimble MA. Heathcock CH. J. Org. Chem. 1993, 58: 5261

16b Baran PS. Guerrero CA. Corey EJ. Org. Lett. 2003, 5: 1999

17 Waser J. Carreira EM. J. Am. Chem. Soc. 2004, 126: 5676

18 Zatsgendler I. Leblanc Y. Bernstein M. Tetrahedron Lett. 1993, 34: 2441

19 Powers JC. Carroll DL. Biochem. Biophys. Res. Commun. 1975, 67: 639

20 Powers JC. Gupton BF. Methods Enzymol. 1977, 46: 208

21a Rosini G. Medici A. Soverini M. Synthesis 1979, 789

21b Calabretta R. Gallina C. Giordano C. Synthesis 1991, 536

22 Dutta AS. Morley JS. J. Chem. Soc., Perkin Trans. 1 1975, 1712

23 Kurtz AN. Niemann CJ. J. Org. Chem. 1961, 26: 1843