CuI/l-Proline-Catalyzed Coupling Reactions of Vinyl Bromides with Activated Methylene Compounds

Lin Pei; Weixing Qian

doi:10.1055/s-2006-944227

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2006(11): 1719-1723
DOI: 10.1055/s-2006-944227

LETTER

CuI/l-Proline-Catalyzed Coupling Reactions of Vinyl Bromides with Activated Methylene Compounds

Lin Pei, Weixing Qian*
Department of Chemistry, Zhejiang University, Campus Yuquan, Hangzhou, Zhejiang 310028, P. R. of China
e-Mail: weixingqian@zju.edu.cn;

Further Information

Publication History

Received 6 March 2006
Publication Date:
04 July 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The Ullmann-type coupling reaction of vinyl bromides and activated methylene compounds under CuI/l-proline in DMSO, at 90 °C in the presence of Cs₂CO₃ gives the corresponding vinyl compounds in moderate to good yields. This is a good method for preparing compounds with multiple functional groups including double bonds, carbonyls, and/or esters.

Key words

carbon-carbon coupling reaction - Ullmann-type reaction - activated methylene compounds - copper iodide - vinyl bromide

References and Notes

1a Lorsbach BA. Kurth MJ. Chem. Rev. 1999, 99: 1549

Google Scholar
1b Sammelson RE. Kurth MJ. Chem. Rev. 2000, 101: 137

Google Scholar
1c Dilman AD. Ioffe SL. Chem. Rev. 2003, 103: 733

Google Scholar
1d Casiraghi G. Zanardi F. Appendino G. Rassu G. Chem. Rev. 2000, 100: 1929

Google Scholar
1e Luh T.-Y. Leung M.-K. Wong K.-T. Chem. Rev. 2000, 100: 3187

Google Scholar
1f Li C.-J. Chem. Rev. 2005, 105: 3095

Google Scholar
1g Fagnou K. Lautens M. Chem. Rev. 2003, 103: 169

Google Scholar
1h Svedendahl M. Hult K. Berglund P. J. Am. Chem. Soc. 2005, 127: 17988

Google Scholar
1i Fillion E. Carson RJ. Trépanier VE. Goll JM. Remorova AA. J. Am. Chem. Soc. 2004, 126: 15354

Google Scholar
2a Jørgensen M. Lee S. Liu X. Wolkowski JP. Hartwig JF. J. Am. Chem. Soc. 2002, 124: 12557

Google Scholar
2b You J. Verkade JG. Angew. Chem. Int. Ed. 2003, 42: 5051

Google Scholar
2c You J. Verkade JG. J. Org. Chem. 2003, 68: 8003

Google Scholar
2d Beare NA. Hartwig JF. J. Org. Chem. 2002, 67: 541

Google Scholar
2e Stauffer SR. Beare NA. Stambuli JP. Hartwig JF. J. Am. Chem. Soc. 2001, 123: 4641

Google Scholar
2f Fox JM. Huang X. Chieffi A. Buchwald SL. J. Am. Chem. Soc. 2000, 122: 1360

Google Scholar
2g Moradi WA. Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7996

Google Scholar
2h Terao Y. Fukuoka Y. Satoh T. Miura M. Nomura M. Tetrahedron Lett. 2002, 43: 101

Google Scholar
2i Lloyd-Jones GC. Angew. Chem. Int. Ed. 2002, 41: 953

Google Scholar
2j Kashin AN. Mitin AV. Beletskaya IP. Wife R. Tetrahedron Lett. 2002, 43: 2539

Google Scholar
2k Hamada T. Chieffi A. Åhman J. Buchwald SL. J. Am. Chem. Soc. 2002, 124: 1261

Google Scholar
2l Viciu MS. Germaneau RF. Nolan SP. Org. Lett. 2002, 4: 4053

Google Scholar
3a Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev. 2002, 102: 1359

Article in Thieme Connect Google Scholar
3b Ley SV. Thomas AW. Angew. Chem. Int. Ed. 2003, 42: 5400

Article in Thieme Connect Google Scholar
3c Kunz K. Scholz U. Ganzer D. Synlett 2003, 2428

Article in Thieme Connect Google Scholar
3d Hennessy EJ. Buchwald SL. Org. Lett. 2002, 4: 269

Article in Thieme Connect Google Scholar
3e Ma D. Liu F. Chem. Commun. 2004, 1934

Article in Thieme Connect Google Scholar
3f Zhang S. Zhang D. Liebeskind LS. J. Org. Chem. 1997, 62: 2312

Article in Thieme Connect Google Scholar
3g Bates CG. Saejueng P. Venkataraman D. Org. Lett. 2004, 6: 1441

Article in Thieme Connect Google Scholar
3h Jiang Y. Wu N. Wu H. He M. Synlett 2005, 2731

Article in Thieme Connect Google Scholar
4a Hurtley WRH. J. Chem. Soc. 1929, 1870

Crossref Google Scholar
4b Bruggink A. Ray SJ. McKillop A. Org. Synth. 1978, 58: 52

Crossref Google Scholar
4c Bryson TA. Stewart JJ. Gibson JM. Thomas PS. Berch JK. Green Chem. 2003, 5: 174

Crossref Google Scholar
4d Bruggink A. McKillop A. Tetrahedron 1975, 31: 2607

Crossref Google Scholar
4e Lindley J. Tetrahedron 1984, 40: 1433

Crossref Google Scholar
4f Shinkwin AE. Whish WJD. Threadgill MD. Bioorg. Med. Chem. 1999, 7: 297

Crossref Google Scholar
5a Hang HC. Drotleff E. Elliott GI. Ritsema TA. Konopelski JP. Synthesis 1999, 398

Google Scholar
5b Suzuki H. Yi Q. Inoue J. Kusume K. Ogawa T. Chem. Lett. 1987, 887

Google Scholar
5c Suzuki H. Kobayashi T. Osuka A. Chem. Lett. 1983, 589

Google Scholar
6 Okuro K. Furuune M. Miura M. Nomura M. J. Org. Chem. 1993, 58: 7606

Crossref Google Scholar
7a Ma D. Cai Q. Xie X. Synlett 2005, 1767

Crossref PubMed Google Scholar
7b Zhu W. Ma D. J. Org. Chem. 2005, 70: 2696

Crossref PubMed Google Scholar
7c Cai Q. Zhu W. Zhang H. Zhang Y. Ma D. Synthesis 2005, 496

Crossref PubMed Google Scholar
7d Ma D. Cai Q. Zhang H. Org. Lett. 2003, 5: 2453

Crossref PubMed Google Scholar
7e Ma D. Cai Q. Org. Lett. 2003, 5: 3799

Crossref PubMed Google Scholar
7f Ma D. Cai Q. Synlett 2004, 128

Crossref PubMed Google Scholar
7g Pan X. Cai Q. Ma D. Org. Lett. 2004, 6: 1809

Crossref PubMed Google Scholar
7h Zhu W. Ma D. Chem. Commun. 2004, 888

Crossref PubMed Google Scholar
7i Zhang H. Cai Q. Ma D. J. Org. Chem. 2005, 70: 5164

Crossref PubMed Google Scholar
7j Xie X. Cai G. Ma D. Org. Lett. 2005, 7: 4693

Crossref PubMed Google Scholar
8a Marcoux J.-F. Doye S. Buchwald SL. J. Am. Chem. Soc. 1997, 119: 10539

Crossref PubMed Google Scholar
8b Kiyomori A. Marcoux JF. Buchwald SL. Tetrahedron Lett. 1999, 40: 2657

Crossref PubMed Google Scholar
8c Wolter M. Klapars A. Buchwald SL. Org. Lett. 2001, 3: 3803

Crossref PubMed Google Scholar
8d Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc. 2001, 123: 7727

Crossref PubMed Google Scholar
8e Antilla JC. Buchwald SL. Org. Lett. 2001, 3: 2077

Crossref PubMed Google Scholar
9 Wang Z. Bao W. Jiang Y. Chem. Commun. 2005, 2849

Crossref Google Scholar
10a Wan Z. Jones CD. Koenig TM. Pu YJ. Mitchell D. Tetrahedron Lett. 2003, 44: 8257

Crossref Google Scholar
10b Willis MC. Taylor D. Gillmore AT. Chem. Commun. 2003, 2222

Crossref Google Scholar
10c Nordmann G. Buchwald SL. J. Am. Chem. Soc. 2003, 125: 4978

Crossref Google Scholar

11

Typical Procedure: A two-necked flask was charged with vinyl bromide (0.5 mmol), CuI (0.05 mmol), l-proline (0.1 mmol), and Cs₂CO₃ (1.0 mmol), evacuated, and backfilled with nitrogen. The activated methylene compound (1.0 mmol) and DMSO (2 g) were added under nitrogen. The flask was immersed in a pre-heated oil bath, and the reaction mixture was stirred at 90 °C until the conversion was complete (detected by TLC). The cooled mixture was purified by column chromatography on silica gel (PE-EtOAc, 10:1 to 5:1) to provide the desired product.
( E )-3-Styrylpentane-2,4-dione (Table [2] , entry 1): IR (film): 3429.1, 3062.4, 3029.7, 2927.2, 1709.1, 1600.9, 1495.2, 1450.2, 1357.4, 1204.9, 1143.7, 1025.8, 976.2, 751.0, 699.4 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.21 (6 H, s, CH₃), 6.41 (1 H, d, J = 16.4 Hz, CH), 6.74 (1 H, d, J = 16.4 Hz, CH), 7.34-7.43 (5 H, m, ArH) 16.75 (1 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 24.23, 111.30, 122.73, 126.05, 127.65, 128.66, 134.16, 137.02, 191.16. MS (70 eV): m/z (%) = 209.0992 (43), 176.0828 (100). HRMS (70 eV): m/z calcd for C₁₃H₁₄O₂, 202.0988; found: 202.0992.
( E )-Ethyl-2-acetyl-4-phenylbut-3-enoate (Table [2] , entry 2): IR (film): 3459.6, 3061.9, 3029.3, 2982.8, 2936.7, 1732.5, 1599.7, 1449.9, 1368.5, 1247.5, 1079.8, 1018.0, 757.9, 699.6 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (1.2 H, t, J = 7.2 Hz, CH₃), 1.35 (1.8 H, t, J = 7.2 Hz, CH₃), 2.22 (1.8 H, s, CH₃), 2.28 (1.2 H, s, CH₃), 4.23 (0.8 H, q, J = 7.2 Hz, CH₂), 4.24 (0.4 H, s, CH), 4.30 (1.2 H, q, J = 7.2 Hz, CH₂), 6.42 (0.4 H, dd, J = 16.0, 9.2 Hz, CH), 6.58 (0.4 H, d, J = 16.0 Hz, CH), 6.60 (0.6 H, d, J = 16.0 Hz, CH), 6.74 (0.6 H, d, J = 16.0 Hz, CH), 7.31-7.42 (5 H, m, ArH), 13.37 (0.6 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 14.03, 14.19, 20.28, 28.45, 60.92, 61.68, 63.87, 101.28, 120.99, 121.57, 125.91, 126.56, 127.04, 128.18, 128.54, 128.60, 130.62, 135.36, 135.99, 138.03, 168.41, 172.63, 174.64, 201.38. MS (70 eV): m/z (%) = 232.1099 (84) [M⁺], 205.0856 (100), 190.0986 (97), 171.0440 (62). HRMS (70 eV): m/z calcd for C₁₄H₁₆O₃: 232.1094; found: 232.1099.
( E )-Diethyl-2-styrylmalonate (Table [2] , entry 3): IR (film): 2983.3, 2938.7, 2909.6, 1732.6, 1465.2, 1449.4, 1369.3, 1258.4, 1151.3, 1033.8, 967.1, 857.8, 757.9, 692.7 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.28 (6 H, t, J = 7.2 Hz, CH₃), 4.17-4.26 (5 H, m, CH₂, CH), 6.42 (1 H, dd, J = 16.0, 8.8 Hz, CH), 6.59 (1 H, d, J = 16.0 Hz, CH), 7.27-7.42 (5 H, m, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 13.96, 55.86, 61.40, 120.84, 126.56, 128.01, 128.49, 134.96, 136.04, 167.96. MS (70 eV): m/z (%) = 262.1204 (100) [M⁺], 190.0989 (53), 189.0911 (28). HRMS (70 eV): m/z calcd for C₁₅H₁₈O₄: 262.1200; found: 262.1204.
( E )-3-(4-Chlorostyryl)pentane-2,4-dione (Table [2] , entry 5): IR (film): 3055.4, 2913.6, 1443.6, 1071.7, 748.8, 692.1 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.22 (6 H, s, CH₃), 6.36 (1 H, d, J = 16.4 Hz, CH), 6.72 (1 H, d, J = 16.4 Hz, CH), 7.30-7.36 (4 H, m, ArH) 16.78 (1 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 24.27, 111.12, 123.38, 127.23, 128.78, 132.74, 133.22, 135.51, 191.20. MS: m/z (%) = 236.0601 (100) [M⁺], 238.0575 (35) [M⁺ + 2], 221.0365 (30). HRMS (70 eV): m/z calcd for C₁₃H₁₃ClO₂: 236.0599; found: 236.0601.
( E )-Ethyl-2-acetyl-4-(4-chlorophenyl)but-3-enoate (Table [2] , entry 6): IR (film): 3471.5, 2982.2, 2929.3, 1722.1, 1592.1, 1491.8, 1368.8, 1247.0, 1092.0, 1013.7, 974.4, 828.9 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.30 (1.2 H, t, J = 7.2 Hz, CH₃), 1.36 (1.8 H, t, J = 7.2 Hz, CH₃), 2.22 (1.8 H, s, CH₃), 2.29 (1.2 H, s, CH₃), 4.24 (0.8 H, q, J = 7.2 Hz, CH₂), 4.25 (0.4 H, s, CH), 4.30 (1.2 H, q, J = 7.2 Hz, CH₂), 6.40 (0.4 H, dd, J = 16.0, 8.8 Hz, CH), 6.52 (0.4 H, d, J = 16.0 Hz, CH), 6.56 (0.6 H, d, J = 16.0 Hz, CH), 6.71 (0.6 H, d, J = 16.0 Hz, CH), 7.27-7.34 (4 H, m, ArH), 13.41 (0.6 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 14.04, 14.22, 20.32, 28.56, 61.02, 61.81, 63.72, 76.61, 101.10, 121.67, 122.15, 127.06, 127.77, 128.66, 128.79, 129.09, 132.50, 134.07, 134.48, 136.58, 168.27, 172.53, 175.02, 201.13. MS (70 eV): m/z (%) = 216.1146 (100) [M⁺], 268.0679 (38) [M⁺ + 2], 240.0554 (40), 224.0598 (80), 220.0288 (74), 207.0022 (42), 205.0052 (98). HRMS (70 eV): m/z calcd for C₁₄H₁₅ClO₃: 266.0704; found: 216.1146.
( E )-Diethyl-2-(4-chlorostyryl)malonate (Table [2] , entry 7): IR (film): 2983.7, 2934.6, 1732.7, 1492.2, 1465.7, 1446.6, 1369.5, 1256.7, 1151.2, 1094.7, 1035.1, 968.7, 821.9 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (6 H, t, J = 7.2 Hz, CH₃), 4.16-4.26 (5 H, m, CH₂, CH), 6.40 (1 H, dd, J = 16.0, 8.8 Hz, CH), 6.55 (1 H, d, J = 16.0 Hz, CH), 7.28-7.35 (4 H, m, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 13.89, 55.66, 61.33, 121.49, 127.71, 128.59, 133.65, 134.50, 167.73. MS (70 eV): m/z (%) = 296.0818 (100) [M⁺], 298.0784 (32) [M⁺ + 2], 224.0600(80), 223.0522 (35), 178.0181 (40).
HRMS (70 eV): m/z calcd for C₁₅H₁₇ClO₄: 296.0810; found: 296.0818.
( E )-3-(4-Methylstyryl)pentane-2,4-dione (Table [2] , entry 8): IR (film): 3055.4, 2913.6, 1443.6, 1071.7, 748.8, 692.1 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.21 (6 H, s, CH₃), 2.36 (3 H, s, CH₃), 6.38 (1 H, d, J = 16.0 Hz, CH), 6.68 (1 H, d, J = 16.0 Hz, CH), 7.16 (2 H, d, J = 8.0 Hz, ArH), 7.16 (2 H, d, J = 8.0 Hz, ArH), 16.71 (1 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 21.18, 24.23, 111.40, 121.72, 125.99, 129.36, 134.17, 134.24, 137.61, 191.13. MS (70 eV): m/z (%) = 216.1148 (100) [M⁺], 201.0912 (61). HRMS (70 eV): m/z calcd for C₁₄H₁₆O₃: 216.1145; found: 216.1148.
( E )-Ethyl-2-acetyl-4- p- tolylbut-3-enoate (Table [2] , entry 9): IR (film): 3459.1, 2981.7, 2923.5, 2868.0, 1721.8, 1639.5, 1604.2, 1513.6, 1369.4, 1245.6, 1061.4, 1019.3, 968.6, 860.4, 817.5 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.29 (1.2 H, t, J = 7.2 Hz, CH₃), 1.34 (1.8 H, t, J = 7.2 Hz, CH₃), 2.21 (1.8 H, s, CH₃), 2.27 (1.2 H, s, CH₃), 2.34 (3 H, s, CH₃), 4.23 (0.8 H, q, J = 7.2 Hz, CH₂), 4.24 (0.3 H, s, CH), 4.28 (1.2 H, q, J = 7.2 Hz, CH₂), 6.36 (0.4 H, dd, J = 16.0, 8.8 Hz, CH), 6.54 (0.4 H, d, J = 16.0 Hz, CH), 6.55 (0.6 H, d, J = 16.0 Hz, CH), 6.68 (0.6 H, d, J = 16.0 Hz, CH), 7.13 (2 H, d, J = 8.0 Hz, ArH), 7.29-7.31 (2 H, m, ArH), 13.34 (0.6 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 14.02, 14.19, 20.23, 21.10, 21.17, 28.38, 60.85, 61.61, 63.91, 101.33, 119.90, 120.58, 125.82, 126.46, 129.22, 129.27, 130.66, 133.24, 135.22, 135.25, 136.85, 138.10, 168.51, 172.67, 174.32, 201.51. MS (70 eV): m/z (%) = 246.1254 (72) [M⁺], 204.1145 (38), 200.0832 (77), 185.0596 (100), 158.0727 (27). HRMS (70 eV): m/z calcd for C₁₅H₁₈O₃: 246.1250; found: 246.1254.
( E )-Diethyl-2-(4-methylstyryl)malonate (Table [2] , entry 10): IR (film): 2982.2, 2937.9, 1732.6, 1513.8, 1463.9, 1446.3, 1368.5, 1293.0, 1257.3, 1177.2, 1096.2, 1032.1, 968.5, 862.0, 812.0 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.28 (6 H, t, J = 7.2 Hz, CH₃), 2.33 (3 H, s, CH₃), 4.16 (1 H, d, J = 9.2 Hz, CH), 4.23 (4 H, q, J = 7.2 Hz, CH₂), 6.42 (1 H, dd, J = 16.0, 9.2 Hz, CH), 6.55 (1 H, d, J = 16.0 Hz, CH), 7.13 (2 H, d, J = 8.0 Hz, ArH), 7.31 (2 H, d, J = 8.0 Hz, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 14.01, 21.19, 55.94, 61.73, 119.79, 126.50, 129.22, 133.31, 134.89, 137.95, 168.12. MS (70 eV): m/z (%) =(100) [M⁺], 204.1147 (26), 203.1071 (28), 157.0647 (21), 129.0698 (51). HRMS (70 eV): m/z calcd for C₁₆H₂₀O₄: 276.1356; found: 276.1363.
( E )-3-(4-Methoxystyryl)pentane-2,4-dione (Table [2] , entry 11): IR (film): 3055.4, 2913.6, 1443.6, 1071.7, 748.8, 692.1 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.21 (6 H, s, CH₃), 2.96 (3 H, s, CH₃), 6.35 (1 H, d, J = 16.0 Hz, CH), 6.59 (1 H, d, J = 16.0 Hz, CH), 6.89-6.91 (2 H, m, ArH), 7.35-7.37 (2 H, m, ArH), 16.68 (1 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 24.24, 55.34, 111.47, 114.14, 120.57, 127.29, 130.23, 133.88, 140.17, 191.10. MS (70 eV): m/z (%) = 232.1099 (100) [M⁺], 204.0782 (63), 133.0648 (37). HRMS (70 eV): m/z calcd for C₁₄H₁₆O₃: 232.1094; found: 232.1099.
( E )-3-(1-Phenylprop-1-en-2-yl)pentane-2,4-dione (Table [2] , entry 13): IR (film): 3055.4, 2913.6, 1443.6, 1071.7, 748.8, 692.1 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.99 (2 H, s, CH₃), 2.05 (3 H, d, J = 1.2 Hz, CH₃), 2.13 (4 H, s, CH₃), 6.42 (0.65 H, s, CH), 6.52 (0.35 H, s, CH), 7.18-7.40 (5 H, m, ArH), 16.40 (0.65 H, s, OH), 16.50 (0.35 H, s, OH). ¹³C NMR (100 MHz, CDCl₃): δ = 20.31, 22.84, 23.17, 27.05, 113.13, 118.18, 126.83, 126.92, 127.73, 128.25, 128.45, 128.64, 131.01, 132.60, 133.04, 133.46, 137.03, 137.34, 189.87, 190.14. MS (70 eV): m/z (%) = 216.1146 (100) [M⁺], 201.0912 (87), 173.0961 (25). HRMS (70 eV): m/z calcd for C₁₄H₁₆O₂: 216.1145; found: 216.1146.