Efficient Copper-Catalyzed Chemo Selective Conjugate Addition of Aliphatic Amines to α,β-Unsaturated Compounds in Water

Li-Wen Xu; Jing-Wei Li; Chun-Gu Xia; Shao-Lin Zhou; Xiao-Xue Hu

doi:10.1055/s-2003-42125

LETTER

Efficient Copper-Catalyzed Chemo Selective Conjugate Addition of Aliphatic Amines to α,β-Unsaturated Compounds in Water

Li-Wen Xu, Jing-Wei Li, Chun-Gu Xia*, Shao-Lin Zhou, Xiao-Xue Hu
State key laboratory of Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China
Fax: +86(931)8277088; e-Mail: cgxia@ns.lzb.ac.cn;

Abstract

All articles of this category

Abstract

The first environmentally benign, highly efficient, conjugate addition of aliphatic amines to α,β-unsaturated compounds catalyzed by simple copper salts in the green solvent, water is described.

Key words

copper - conjugate addition - α,β-unsaturated compounds - amines - water

Full Text

References

<A NAME="RU18803ST-1A">1a</A> Muller TE. Beller M. Chem. Rev. 1998, 98: 675

<A NAME="RU18803ST-1B">1b</A> Kim YK. Livinghouse T. Horino Y. J. Am. Chem. Soc. 2003, 125: 9560

<A NAME="RU18803ST-1C">1c</A> Nakamura I. Bajracharya GB. Yamamoto Y. J. Org. Chem. 2003, 68: 2297

<A NAME="RU18803ST-2">2</A> Han LB. Tanaka M. Chem. Commun. 1999, 395

<A NAME="RU18803ST-3A">3a</A> Arredondo VM. Tian S. McDonald FE. Marks TJ. J. Am. Chem. Soc. 1999, 121: 3633

<A NAME="RU18803ST-3B">3b</A> Dorta R. Egli P. Zurcher F. Togni A. J. Am. Chem. Soc. 1997, 119: 10857

<A NAME="RU18803ST-4A">4a</A> The Organic Chemistry of β-Lactams George GI. VCH Publishers; New York: 1993.

<A NAME="RU18803ST-4B">4b</A> Cardillo G. Tomasini C. Chem. Soc. Rev. 1996, 117

<A NAME="RU18803ST-4C">4c</A> Drury WJ. Ferraris D. Cox C. Young B. Leckta T. J. Am. Chem. Soc. 1998, 120: 11006

<A NAME="RU18803ST-4D">4d</A> Hagiwara E. Fujii A. Sodeoka M. J. Am. Chem. Soc. 1998, 120: 2474

<A NAME="RU18803ST-4E">4e</A> Fustero S. Pina B. Salavert E. Navarro A. Ramirez de Arellano MC. Fuentes AS. J. Org. Chem. 2002, 67: 4667

<A NAME="RU18803ST-5A">5a</A> Arend M. Westermann B. Risch N. Angew. Chem. Int. Ed. 1998, 37: 1045

<A NAME="RU18803ST-5B">5b</A> Sibi MP. Shay JJ. Liu M. Jasperse CP. J. Am. Chem. Soc. 1998, 120: 6615

<A NAME="RU18803ST-6A">6a</A> Gao Y. Sharpless KB. J. Org. Chem. 1988, 53: 4081

<A NAME="RU18803ST-6B">6b</A> Shaikh NS. Deshpande VH. Bedekar AV. Tetrahedron 2001, 57: 9045

<A NAME="RU18803ST-7A">7a</A> Adrian JC. Snapper ML. J. Org. Chem. 2003, 68: 2143

<A NAME="RU18803ST-7B">7b</A> Ambhaikar NB. Snyder JP. Liotta DC. J. Am. Chem. Soc. 2003, 125: 3690

<A NAME="RU18803ST-8A">8a</A> Myers JK. Jacobsen EN. J. Am. Chem. Soc. 1999, 121: 8959

<A NAME="RU18803ST-8B">8b</A> Horstmann TE. Guerin DJ. Miller SJ. Angew. Chem. Int. Ed. 2000, 39: 3635

<A NAME="RU18803ST-8C">8c</A> Sibi MP. Liu M. Org. Lett. 2001, 3: 4181

<A NAME="RU18803ST-8D">8d</A> Sibi MP. Gorikunti U. Liu M. Tetrahedron 2002, 58: 8357

<A NAME="RU18803ST-8E">8e</A> Bhuniya D. Mohan S. Narayanan S. Synthesis 2003, 1018

<A NAME="RU18803ST-9">9</A> Kawatsura M. Hartwig JF. Organometallics 2001, 20: 1960

<A NAME="RU18803ST-10">10</A> Leh TP. Wei LL. Synlett 1998, 975

<A NAME="RU18803ST-11">11</A> Bartoli G. Bosco M. Marcantoni E. Pertrini M. Sambri L. Torregiani E. J. Org. Chem. 2001, 66: 9052

<A NAME="RU18803ST-12">12</A> Srivastava N. Banik BK. J. Org. Chem. 2003, 68: 2109

<A NAME="RU18803ST-13">13</A> Varala R. Alam MM. Adapa SR. Synlett 2003, 720

<A NAME="RU18803ST-14A">14a</A> Xu LW. Xia CG. Hu XX. Chem. Commun. 2003, 2570

<A NAME="RU18803ST-14B">14b</A> Xu LW. Xia CG. Li JW. Zhou SL. Synlett 2003, in press

<A NAME="RU18803ST-15A">15a</A> Wei C. Li CJ. J. Am. Chem. Soc. 2002, 124: 5638

<A NAME="RU18803ST-15B">15b</A> Wei C. Li CJJ. Am. Chem. Soc. 2003, 125: 9584

<A NAME="RU18803ST-15C">15c</A> Bose DS. Fatima L. Mereyala HB. J. Org. Chem. 2003, 68: 587

<A NAME="RU18803ST-15D">15d</A> Yi CS. Yun SY. He Z. Organometallics 2003, 22: 3031

<A NAME="RU18803ST-16">16</A> Kobayashi S. Manabe AK. Acc. Chem. Res. 2002, 35: 209

<A NAME="RU18803ST-17A">17a</A> Nagano Y. Orita A. Otera J. Adv. Synth. Catal. 2003, 345: 643

<A NAME="RU18803ST-17B">17b</A> Bartoli G. Bosco M. Dalpozzo R. Marcantoni E. Massaccesi M. Rinaldi S. Sambri L. Synlett 2003, 39

<A NAME="RU18803ST-18A">18a</A> Keh CCK. Wei C. Li CJ. J. Am. Chem. Soc. 2003, 125: 4062

<A NAME="RU18803ST-18B">18b</A> Doncaster JR. Ryan H. Whitehead RC. Synlett 2003, 651

<A NAME="RU18803ST-18C">18c</A> Iimura S. Nobutou D. Manabe K. Kobayashi S. Chem. Commun. 2003, 1644

<A NAME="RU18803ST-18D">18d</A> Li CJ. Acc. Chem. Res. 2002, 35: 533

<A NAME="RU18803ST-18E">18e</A> Lindström UM. Chem. Rev. 2002, 102: 2751

<A NAME="RU18803ST-19">19</A> Furukawa M. Okawara T. Terawaki Y. Chem. Pharm. Bull. 1977, 25: 1319

<A NAME="RU18803ST-20">20</A> D’Angelo J. Maddaluno J. J. Am. Chem. Soc. 1986, 108: 8112

<A NAME="RU18803ST-21">21</A> Jenner G. Tetrahedron Lett. 1995, 36: 233

<A NAME="RU18803ST-22">22</A> Matsubara S. Yoshioka M. Utimoto K. Chem. Lett. 1994, 827

General Procedure for the aza-Michael Addition Reactions. A mixture of amine (1.2 mmol), α,β-unsaturated compound (1 mmol) and copper salts (5 mol%) in acetonitrile/H₂O (1/1) or H₂O was kept at r.t. under vigorous stirring for 12 h. After completion of the reaction, the reaction mixture was extracted with EtOAc and purified by using column chromatography on silical gel to obtain pure product. All the known compounds were fully characterized by GC-MS (Agilent 6890N GC/5973N MS, HP-5MS) and usual spectral methods.