Cellulose-Supported Copper(0) Catalyst for Aza-Michael Addition

Abstract

Cellulose-supported copper(0) efficiently catalyzes the aza-Michael reaction of N-nucleophiles, such as amines and imidazoles with α,β-unsaturated compounds to produce the corresponding β-amino compounds and N-substituted imidazoles in excellent yields. The reactions are facile and the recovered catalyst is used for several cycles with consistent activity.

cellulose - copper - aza-Michael - amines - imidazoles - α,β-unsaturated compounds - β-amino compounds - N-substituted imidazoles

References and Notes

<A NAME="RD06806ST-1A">1a</A> Bartoli G. Cimarelli C. Marcantoni E. Palmieri G. Petrini M. J. Org. Chem.  1994,  59:  5328 

<A NAME="RD06806ST-1B">1b</A> Wang YF. Izawa T. Kobayashi S. Ohno M. J. Am. Chem. Soc.  1982,  104:  6465 

<A NAME="RD06806ST-1C">1c</A> Hashiguchi S. Kawada A. Natsugari H. J. Chem. Soc., Perkin Trans. 1  1991,  2435 

<A NAME="RD06806ST-2A">2a</A> Hayashi Y. Rode JJ. Corey EJ. J. Am. Chem. Soc.  1996,  118:  5502 

<A NAME="RD06806ST-2B">2b</A> Eliel EL. He XC. J. Org. Chem.  1990,  55:  2114 

<A NAME="RD06806ST-3A">3a</A> Traxler P. Trinks U. Buchdunger E. Mett H. Meyer T. Mueller M. Regenass U. Rosel J. Lydon N. J. Med. Chem.  1995,  38:  2441 

<A NAME="RD06806ST-3B">3b</A> Cardillo G. Tomasini C. Chem. Soc. Rev.  1996,  117 

<A NAME="RD06806ST-3C">3c</A> Fustero S. Pina B. Salavert E. Navarro A. Ramirez de Arellano MC. Fuentes AS. J. Org. Chem.  2002,  67:  4667 

<A NAME="RD06806ST-3D">3d</A> Nezhad AK. Rad MNS. Hakimelahi GH. Mokhtari B. Tetrahedron  2002,  58:  10341 

<A NAME="RD06806ST-4A">4a</A> Lin Y. Junhua Z. Huangshu L. Xiaomei L. Mingxiao Z. Org. Prep. Proced. Int.  1991,  23:  673 

<A NAME="RD06806ST-4B">4b</A> Graul A. Castaner J. Drugs Future  1997,  22:  956 

<A NAME="RD06806ST-4C">4c</A> Corey EJ. Reichard GA. Tetrahedron Lett.  1989,  30:  5207 

<A NAME="RD06806ST-5">5</A> Arend M. Westermann B. Risch N. Angew. Chem. Int. Ed.  1998,  37:  1044 

<A NAME="RD06806ST-6A">6a</A> Bull SD. Davies SGS. Ballester D. Fenton G. Kelly PM. Smith AD. Synlett  2000,  1257 

<A NAME="RD06806ST-6B">6b</A> Davies SG. McCarthy TD. Synlett  1995,  700 

<A NAME="RD06806ST-7">7</A> Rosenthal D. Brandrup G. Davis KH. Wall ME. J. Org. Chem.  1965,  30:  3689 

<A NAME="RD06806ST-8">8</A> Kawatsura M. Hartwig JF. Organometallics  2001,  20:  1960 

<A NAME="RD06806ST-9">9</A> Jenner G. Tetrahedron Lett.  1995,  36:  233 

<A NAME="RD06806ST-10">10</A> Loh T.-P. Wei L.-L. Synlett  1998,  975 

<A NAME="RD06806ST-11">11</A> Bartoli G. Bosco M. Marcantoni E. Pertrini M. Sanbri L. Torregiani E. J. Org. Chem.  2001,  66:  9052 

<A NAME="RD06806ST-12A">12a</A> Srivastava N. Banik BK. J. Org. Chem.  2003,  68:  2109 

<A NAME="RD06806ST-12B">12b</A> Varala R. Alam MM. Adapa SR. Synlett  2003,  720 

<A NAME="RD06806ST-12C">12c</A> Reboule I. Gil R. Collin J. Tetrahedron Lett.  2005,  46:  7761 

<A NAME="RD06806ST-13">13</A> Xu LW. Li JW. Xia CG. Zhou SL. Hu XX. Synlett  2003,  2425 

<A NAME="RD06806ST-14">14</A> Xu LW. Li L. Xia CG. Helv. Chim. Acta  2004,  87:  1522 

<A NAME="RD06806ST-15">15</A> Azizi N. Saidi MR. Tetrahedron  2004,  60:  383 

<A NAME="RD06806ST-16A">16a</A> Shaikh NS. Despande VH. Bedekar AV. Tetrahedron  2001,  57:  9045 

<A NAME="RD06806ST-16B">16b</A> Kantam ML. Neelima B. Venkat Reddy Ch. J. Mol. Catal. A: Chem.  2005,  241:  147 

<A NAME="RD06806ST-17A">17a</A> Yang L. Xu L.-W. Xia CG. Tetrahedron Lett.  2005,  46:  3279 

<A NAME="RD06806ST-17B">17b</A> Zhang H. Zhang Y. Liu L. Xu H. Wang Y. Synthesis  2005,  2129 

<A NAME="RD06806ST-17C">17c</A> Bartoli G. Bartolacci M. Giuliani A. Marcantoni E. Massaccesi M. Torregiani E. J. Org. Chem.  2005,  70:  169 

<A NAME="RD06806ST-18A">18a</A> Yadav JS. Reddy BVS. Basak AK. Narsaiah AV. Chem. Lett.  2003,  32:  988 

<A NAME="RD06806ST-18B">18b</A> Xu LW. Li JW. Zhou SL. Xia CG. New J. Chem.  2004,  28:  183 

<A NAME="RD06806ST-18C">18c</A> Kantam ML. Neeraja V. Kavita B. Neelima B. Chaudhuri MK. Hussain S. Adv. Synth. Catal.  2005,  347:  763 

<A NAME="RD06806ST-19">19</A> Green Chemistry and Technology   Clark JH. Macquarrie DJ. Blackwell; Abingdon: 2002. 

<A NAME="RD06806ST-20">20</A> Guibal E. Progr. Polym. Sci.  2005,  30:  71 

<A NAME="RD06806ST-21">21</A> Wei W.-L. Zhu H.-Y. Zhao C.-L. Huang M.-Y. Jiang Y.-Y. React. Funct. Polym.  2004,  59:  33 

<A NAME="RD06806ST-22">22</A> Zhang X. Geng Y. Han B. Ying M.-Y. Huang M.-Y. Jiang YY. Polym. Adv. Technol.  2001,  12:  642 

<A NAME="RD06806ST-23">23</A> Huang K. Xue L. Hu Y.-C. Huang M.-Y. Jiang Y.-Y. React. Funct. Polym.  2002,  50:  199 

<A NAME="RD06806ST-24">24</A> Quignard F. Choplin A. Domard A. Langmuir  2000,  16:  9106 

<A NAME="RD06806ST-25A">25a</A> Reddy KR. Kumar NS. Sreedhar B. Kantam ML. J. Mol. Catal. A: Chem.  2006,  252:  136 

<A NAME="RD06806ST-25B">25b</A> Reddy KR. Kumar NS. Reddy PS. Sreedhar B. Kantam ML. J. Mol. Catal. A: Chem.  2006,  252:  12 

<A NAME="RD06806ST-26">26</A> He J. Kunitake T. Watanabe T. Chem. Commun.  2005,  795 

<A NAME="RD06806ST-27">27</A> Verma AK. Kumar R. Chaudhary P. Saxena A. Shankar R. Mozumdar S. Chandra R. Tetrahedron Lett.  2005,  46:  5229 

<A NAME="RD06806ST-28">28</A>

Typical Experimental Procedure for the Conjugate Addition of Amines to α,β-Unsaturated Compounds: In a typical procedure, α,β-unsaturated compound (1.0 mmol), amine (1.0 mmol) and catalyst (1.2 mol%) were taken in MeOH (5 mL) and stirred at r.t. for the appropriate time. After completion of the reaction as monitored by TLC, the reaction mixture was filtered and washed with MeOH (3 × 5 mL). The resulting reaction mixture was concentrated under reduced pressure. The crude product was purified by column chromatography to afford the pure product. All the products gave satisfactory NMR data and mass spectral data. [9] [11] [15] [17b] [c]

<A NAME="RD06806ST-29A">29a</A> Cai Y. Yao SP. Wu Q. Lin XF. Biotechnol. Lett.  2004,  26:  525 

<A NAME="RD06806ST-29B">29b</A> Cai Y. Wu Q. Xiao YM. Lu DS. Lin XF. J. Biotech.  2006,  121:  330 

<A NAME="RD06806ST-29C">29c</A> Yao SP. Lu DS. Wu Q. Cai Y. Xu SH. Lin XF. Chem. Commun.  2004,  2006 

<A NAME="RD06806ST-30">30</A> Aranda RMM. Cantero EO. Carvantes MLR. Rodriguez MAV. Munoz MAB. Catal. Lett.  2002,  84:  201 

<A NAME="RD06806ST-31">31</A>

Typical Experimental Procedure for the Conjugate Addition of Imidazole to α,β-Unsaturated Compounds: In a typical procedure, α,β-unsaturated compound (1.0 mmol), imidazole (1.0 mmol) and catalyst (3.6 mol%) were taken in toluene (5 mL) and stirred at reflux temperature for 12 h. The resulting reaction mixture was filtered and washed with EtOAc (3 × 5 mL) and concentrated under reduced pressure. The crude product was purified by column chromatography to afford the pure product. All the products gave satisfactory NMR data and mass spectral data. [12a] [29]
tert-Butyl-3-(1H-1-imidazolyl)propanoate (Table [2] , Entry 5): ¹H NMR (200 MHz, CDCl₃): δ = 7.44 (s, 1 H), 6.97 (s, 1 H), 6.87 (s, 1 H), 4.21 (t, J = 6.80 Hz, 2 H), 2.66 (t, J = 6.80 Hz, 2 H), 1.41 (s, 9 H). MS (70 eV): m/z = 196 [M⁺].