CuI-Catalyzed Cross-Coupling Reaction of (E)-Vinyl Bromides with Nitrogen-Containing Heterocycles

Abstract

An efficient and straightforward copper-catalyzed method allowing vinylation of N-nucleophiles with various substituted (E)-vinyl bromides under palladium-free and ligand-free conditions has taken a high yield (up to 95%). Noteworthy is that the double-bond geometry of these vinyl halides was retained with our protocol.

halides - nucleophiles - copper - cross-coupling - heterocycles

References and Notes

1 Negwer M. Organic-Chemical Drugs and their Synonyms: An International Survey   7th ed.:  Akademie; Berlin: 1994. 

2a Ullmann F. Ber. Dtsch. Chem. Ges.  1903,  36:  2382 

2b Lindley J. Tetrahedron  1984,  40:  1433 

2c Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 

2d Taillefer M. Xia N. Ouali A. Angew. Chem. Int. Ed.  2007,  46:  934 

2e Schnürch M. Flasik R. Khan AF. Spina M. Mihovilovic MD. Stanetty P. Eur. J. Org. Chem.  2006,  3283 

3a Altman RA. Buchwald SL. Org. Lett.  2006,  8:  2779 

3b Antilla JC. Baskin JM. Barder TE. Buchwald SL. J. Org. Chem.  2004,  69:  5578 

3c Antilla JC. Klapars A. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  11684 

3d Kwong FY. Klapars A. Buchwald SL. Org. Lett.  2002,  2:  581 

3e Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7727 

3f Kwong FY. Buchwald SL. Org. Lett.  2003,  5:  793 

4a Zhang H. Cai Q. Ma D. J. Org. Chem.  2005,  70:  5164 

4b Ma D. Cai Q. Synlett  2004,  128 

4c Ma D. Cai Q. Zhang H. Org. Lett.  2003,  5:  2453 

4d Ma D. Xia C. Org. Lett.  2001,  3:  2583 

4e Ma D. Zhang Y. Yao J. Wu S. Tao F. J. Am. Chem. Soc.  1998,  120:  12459 

5 Gujadhur RK. Bates CG. Venkataraman D. Org. Lett.  2001,  3:  4315 

6 Liu L. Frohn M. Xi N. Dominguez C. Hungate R. Reider PJ. J. Org. Chem.  2005,  70:  10135 

7 Zhu L. Cheng L. Zhang Y. Xie R. You J. J. Org. Chem.  2007,  72:  2737 

8 Jerphagnon T. van Klink GPM. de Vries JG. van Koten G. Org. Lett.  2005,  7:  5241 

9 Gajare AS. Toyota K. Yoshifuji M. Ozawa F. Chem. Commun.  2004,  1994 

10 Zhang Z. Mao J. Zhu D. Wu F. Chen H. Wan B. Tetrahedron  2006,  62:  4435 

11a Xu L. Mao J. Zhu D. Wu F. Wang R. Wan B. Tetrahedron  2006,  61:  6553 

11b Zhu D. Xu L. Wu F. Wan B. Tetrahedron Lett.  2006,  47:  5781 

12a Lu Z. Twieg RJ. Huang SD. Tetrahedron Lett.  2003,  44:  6289 

12b Lu Z. Twieg RJ. Tetrahedron  2005,  61:  903 

13a Kelkar AA. Patil NM. Chaudhari RV. Tetrahedron Lett.  2002,  43:  7143 

13b Beletskaya IP. Cheprakov AV. Coord. Chem. Rev.  2004,  248:  2337 

14 Rao H. Fu H. Jiang Y. Zhao Y. J. Org. Chem.  2005,  70:  8107 

15 Kwong FY. Buchwald SL. Org. Lett.  2003,  5:  793 

16a Jiang D. Fu H. Jiang Y. Zhao Y. J. Org. Chem.  2007,  72:  672 

16b Xie Y. Pi S. Wang J. Yin D. Li J. J. Org. Chem.  2006,  71:  8324 

16c Cristau HJ. Cellier PP. Spindler JF. Taillefer M. Chem. Eur. J.  2004,  10:  5607 

16d Ma H.-C. Jiang X.-Z. J. Org. Chem.  2007,  72:  8943 

16e Yang M. Liu F. J. Org. Chem.  2007,  72:  8969 

In addition, the copper-catalyzed C-N couplings performed at room temperature have been reported:

16f Shafir A. Buchwald SL. J. Am. Chem. Soc.  2006,  128:  8742 

16g Lv X. Bao W. J. Org. Chem.  2007,  72:  3863 

17a Cristau HJ. Cellier PP. Spindler JF. Taillefer M. Chem. Eur. J.  2004,  10:  5607 

17b Zhang H. Cai Q. Ma D. J. Org. Chem.  2005,  70:  5164 

17c Lv X. Wang Z. Bao W. Tetrahedron  2006,  62:  4756 

17d Rao H. Jin Y. Fu H. Jiang Y. Zhao Y. Chem. Eur. J.  2006,  12:  3636 

17e Xie Y. Pi S. Wang J. Yin D. Li J. J. Org. Chem.  2006,  71:  8324 

17f Liu L. Frohn M. Xi N. Dominguez C. Hungate R. Reider PJ. J. Org. Chem.  2005,  70:  10135 

17g Verma AK. Sing J. Sankar VK. Chaudhary R. Chandra R. Tetrahedron Lett.  2007,  48:  4207 

The selected examples:

18a Kurdaziel K. Glowiak T. J. Coord. Chem.  2002,  55:  327 

18b Branowska D. Synthesis  2003,  2096 

18c Aggarwal VK. De Vicente J. Bonnert RV. J. Org. Chem.  2003,  68:  5119 

18d Mano N. Kim HH. Zhang Y. Heller A. J. Am. Chem. Soc.  2002,  124:  6480 

18e Morita T. Nozawa Y. Nippon Ishinkin Gakkai Zasshi  1990,  31:  363 

19a Tzalis D. Henkelmann J. Heider M. Tetrahedron Lett.  1999,  40:  6193 

19b Hayat S. Rahman A. Choudhary MI. Khan KM. Schumann W. Bayer E. Tetrahedron  2001,  57:  9951 

19c Lam PYS. Vincent G. Clark CG. Deudon S. Jadhav PK. Tetrahedron Lett.  2001,  42:  3415 

19d Cooper G. Irwin WJ. J. Chem. Soc., Perkin Trans. 1  1975,  798 

19e Cooper G. Irwin WJ. J. Chem. Soc., Perkin Trans. 1  1976,  545 

20 Lebedev AY. Izmer VV. Kazyul’kin DN. Beletskaya IP. Voskoboynikov AZ. Org. Lett.  2002,  4:  623 

21 Taillefer M. Ouali A. Renard B. Spindler J.-F. Chem. Eur. J.  2006,  12:  5301 

22 Wang Z. Bao W. Jiang Y. Chem. Commun.  2005,  2849 

23a Mao J. Guo J. Tetrahedron  2008,  64:  1383 

23b Zhu D. Wang R. Mao J. Xu L. Wu F. Wan B. J. Mol. Catal. A: Chem.  2006,  256:  256 

24 Chowdhury S. Roy S. J. Org. Chem.  1997,  62:  199 

25

General Procedure for C-N Coupling Reactions of β-Bromostyrene and Heterocycle Copper(I) iodide (0.1 equiv) and Cs₂CO₃ (2.0 equiv) were added to a screw-capped test tube. The tube was then evacuated and backfilled with argon (3 cycles). N,N-Dimethylformamide (2 mL), nitrogen-containing heterocycles (1.2 equiv; if liquid) and vinyl halide (1.0 equiv; if liquid) were added by syringe at r.t. The tube was again evacuated and backfilled with argon (3 cycles). The mixture was heated to 120 ˚C and stirred for 36-50 h. After cooling to r.t., the mixture was diluted with H₂O, and the combined aqueous phases were extracted three times with EtOAc. The organic layers were combined, dried over Na₂SO₄, and concentrated to yield the crude product, which was further purified by silica gel chromatography, using PE and EtOAc as eluents to provide the desired product.
Characteristic Data of Representative Products Compound 1:^²¹,²² 95%; mp 184-185 ˚C. ^¹H NMR (DMSO-d ₆): δ = 8.02 (s, 1 H, 2-H in imidazole), 7.85 (d, J = 14.4 Hz, 1 H, CH=CHPh), 7.71 (s, 1 H, ArH), 7.26-7.51 (m, 5 H, ArH), 7.05 (s, 1 H, ArH), 7.01-7.05 (m, 2 H, CH=CHPh and ArH). ^¹³C NMR (CDCl₃): δ = 136.1, 134.8, 130.8, 129.4, 128.5, 126.6, 123.1, 119.3, 116.7. HRMS: m/z calcd for C₁₁H₁₀N₂ [M⁺ + H]: 170.0844; found: 170.0843.
Compound 12: 91%; mp 78-80 ˚C. ^¹H NMR (CDCl₃): δ = 7.63 (d, J = 8.0 Hz, 2 H, in ArH), 7.49-7.58 (m, 3 H, in CH=CHPh and ArH), 7.39 (d, J = 8.8 Hz, 2 H, ArH), 7.15-7.30 (m, 2 H, ArH), 6.91 (d, J = 8.8 Hz, 2 H, ArH), 6.64-6.68 (m, 2 H, CH=CHPh and ArH), 3.84 (s, 3 H, CH₃O). ^¹³C NMR (CDCl₃): δ = 159.2, 136.0, 129.5, 129.0, 127.3, 124.3, 123.0, 122.4, 121.6, 121.2, 114. 7, 110.0, 105.3, 55.7. HRMS: m/z calcd for C₁₇H₁₅NO [M⁺ + H]: 249.1154; found: 249.1153.

During the course of our research on the ligand-free C-N coupling reaction, we found the following relevant reports:

26a CuI-catalyzed N-arylation of nitrogen heterocycles with aryl iodides in the presence of n-Bu₄NBr as the phase-transfer catalyst: Chang JWW. Xu X. Chan PWH. Tetrahedron. Lett.  2007,  48:  245 

26b Cu₂O-catalyzed N-arylation of nitrogen nucleophiles: Correa A. Bolm C. Adv. Synth. Catal.  2007,  349:  2673 

26c CuI-catalyzed N-arylation of nitrogen nucleophiles with aryl halides: Zhu L. Guo P. Li G. Lan J. Xie R. You J. J. Org. Chem.  2007,  72:  8535 

(Z)-β-Bromostyrene was synthesized according the references:

27a Kuang C. Senboku H. Tokuda M. Tetrahedron Lett.  2001,  42:  3893 

27b Kuang C. Yang Q. Senboku H. Tokuda M. Tetrahedron  2005,  61:  4043 

27c

Colorless oil. ^¹H NMR (CDCl₃): δ = 7.68 (d, J = 7.2 Hz, 1 H, ArH), 7.30-7.40 (m, 3 H, ArH), 7.06 (d, J = 8.0 Hz, 1 H, CH=CHPh), 6.42 (d, J = 8.0 Hz, 1 H, CH=CHPh).

28

Colorless oil. ^¹H NMR (CDCl₃): δ = 7.48 (s, 1 H, ArH), 7.27-7.29 (m, 3 H, ArH), 7.09-7.12 (m, 2 H, ArH), 7.04 (s, 1 H, ArH), 6.86 (s, 1 H, ArH), 6.74 (d, J = 9.2 Hz, 1 H, CH=CHPh), 6.36 (d, J = 9.2 Hz, 1 H, CH=CHPh). ^¹³C NMR (CDCl₃): δ = 137.4, 134.1, 130.0, 129.1, 128.9, 128.7, 123.8, 122.8, 118.9.

29 Verma AK. Singh J. Sankar VK. Chaudhary R. Chandra R. Tetrahedron Lett.  2007,  48:  4207