Alternate, Easy and Practical Synthesis of Allylamines from Acetyl Derivatives of Baylis-Hillman Adducts Using Methanolic Ammonia

Richa Pathak; Vijay Singh; Som N. Nag; Sanjeev Kanojiya; Sanjay Batra

doi:10.1055/s-2006-926337

PAPER

Alternate, Easy and Practical Synthesis of Allylamines from Acetyl Derivatives of Baylis-Hillman Adducts Using Methanolic Ammonia [1]

Richa Pathak^a, Vijay Singh^a, Som N. Nag^a, Sanjeev Kanojiya^b, Sanjay Batra*^a
^a Medicinal Chemistry Division, Central Drug Research Institute, Lucknow 226001, India
Fax: +91(522)2623405; Fax: +91(522)2623938; e-Mail: batra_san@yahoo.co.uk;
^b SAIF Division, Central Drug Research Institute, Lucknow 226001, India

Abstract

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Abstract

A methanolic ammonia-mediated alternate, easy and practical stereoselective synthesis of allylamines from the acetyl derivatives of Baylis-Hillman adducts is described.

Key words

Baylis-Hillman - allylamine - methanolic ammonia - stereoselective

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References

CDRI Communication No. 6786.

<A NAME="RP12505SS-2A">2a</A> Basavaiah D. Jaganmohan Rao A. Satyanarayana T. Chem. Rev. 2003, 103: 811

<A NAME="RP12505SS-2B">2b</A> Kim JN. Lee KY. Curr. Org. Chem. 2002, 6: 627

<A NAME="RP12505SS-2C">2c</A> Cho HI. Lee SW. Lee K.-J. J. Heterocycl. Chem. 2004, 41: 799

<A NAME="RP12505SS-2D">2d</A> Basavaiah D. Rao JS. Reddy RJ. J. Org Chem. 2004, 69: 7379

<A NAME="RP12505SS-2E">2e</A> Lee CG. Lee KY. GowriSankar S. Kim JN. Tetrahedron Lett. 2004, 45: 7409

<A NAME="RP12505SS-2F">2f</A> Shanmugam P. Rajasingh P. Tetrahedron Lett. 2005, 46: 3369

<A NAME="RP12505SS-2G">2g</A> Shanmugam P. Rajasingh P. Synlett 2005, 939

<A NAME="RP12505SS-2H">2h</A> Hong WP. Lee K.-J. Synthesis 2005, 33

<A NAME="RP12505SS-2I">2i</A> Li J. Wang X. Zhang Y. Synlett 2005, 1039

<A NAME="RP12505SS-2J">2j</A> Heim R. Wiedemann S. Williams CM. Bernhardt PV. Org. Lett. 2005, 7: 1327

<A NAME="RP12505SS-2K">2k</A> Ramachandran PV. Burghardt TE. Reddy MVR. Tetrahedron Lett. 2005, 46: 2121

<A NAME="RP12505SS-2L">2l</A> Lee CG. Lee KY. Lee S. Kim JN. Tetrahedron 2005, 61: 1493

<A NAME="RP12505SS-3A">3a</A> Singh V. Saxena R. Batra S. J. Org. Chem. 2005, 70: 353

<A NAME="RP12505SS-3B">3b</A> Pathak R. Roy AK. Batra S. Synlett 2005, 848

<A NAME="RP12505SS-3C">3c</A> Pathak R. Roy AK. Kanojiya S. Batra S. Tetrahedron Lett. 2005, 46: 5289

<A NAME="RP12505SS-4">4</A> Patra A. Roy AK. Batra S. Bhaduri AP. Synlett 2002, 1819

<A NAME="RP12505SS-5">5</A> Das B. Mahender G. Chowdhury N. Banerjee J. Synlett 2005, 1000

Singh V., Pathak R., Kanojiya S., Batra S.; Synlett; 2005, 2465.

<A NAME="RP12505SS-7A">7a</A> Patra A. Batra S. Kundu B. Joshi BS. Roy R. Bhaduri AP. Synthesis 2001, 276

<A NAME="RP12505SS-7B">7b</A> Cai J. Zhou Z. Zhao G. Tang C. Org. Lett. 2002, 4: 4723

<A NAME="RP12505SS-8A">8a</A> Foucaud A. El Guemmout F. Bull. Soc. Chim. Fr. 1989, 403

<A NAME="RP12505SS-8B">8b</A> Lee JL. Chung YM. Lee KY. Kim JN. Bull. Korean Chem. Soc. 2000, 21: 843

<A NAME="RP12505SS-8C">8c</A> Batra S. Roy AK. Patra A. Bhaduri AP. Surin WS. Raghavan SAV. Sharma P. Kapoor K. Dikshit M. Bioorg. Med. Chem. 2004, 12: 2059

During extensive exploratory studies on the Baylis-Hillman derivatives we have observed that reaction between acetyl derivatives of Baylis-Hillman adducts and primary amines (ca 1-1.5-fold) always lead to tertiary amines (Figure [1] ) as the major product. However, the formation of such an amine can be reduced by using excess amine (ca. 4-fold) and adding acetyl derivative slowly under cold conditions.

Figure 1 Structure of tertiary amines formed in the reaction of primary amines with Baylis-Hillman adducts.

Several experiments using ESI mass spectrometry technique in the presence of NH₄OH and/or NH₄OAc (5-6 mM) were carried out to establish the exact molecular weight of products.