Al/PbCl₂-Catalyzed DMF-Mediated Reductive Coupling of Baylis-Hillman Acetates with Tetrachloromethane

Abstract

2-(2,2,2-Trichloroethyl)alk-2-enoates could be formed in good E-selectivity by the reductive coupling of Baylis-Hillman acetates with tetrachloromethane in good 76-92% yields in the presence of catalytic Al/PbCl₂ and DMF.

Key words

reductive coupling - Baylis-Hillman acetate - tetra­chloromethane - catalytic system

References and Notes

• 1a Bradshaw JWS. Baker R. Howse PE. Nature (London)  1975,  258:  230 
• 1b Garson MJ. Chem. Rev.  1993,  93:  1699 
• 1c D’Auria MV. Minale L. Riccio R. Chem. Rev.  1993,  93:  1839 
• 1d Senokuchi K. Nakai H. Nakayama Y. Odagaki Y. Sakaki K. Kato M. Maruyama T. Miyazaki T. Ito H. Kamiyasu K. Kim S. Kawamura M. Hamanaka N. J. Med. Chem.  1995,  38:  4508 
• 1e Senokuchi K. Nakai H. Nakayama Y. Odagaki Y. Sakaki K. Kato M. Maruyama T. Miyazaki T. Ito H. Kamiyasu K. Kim S. Kawamura M. Hamanaka N. J. Med. Chem.  1995,  38:  2521 
• 1f Watanabe T. Hayashi K. Yoshimatsu S. Sakai K. Takeyama S. Takashima K. J. Med. Chem.  1980,  23:  50 
• 2 Marfat A. McGuirk PR. Helquist P. J. Org. Chem.  1979,  44:  3888 
• 3a Kelly SE. Additions to C-X π-Bonds In Comprehensive Organic Synthesis   Part 1:  Schreiber SL. Pergamon Press; Oxford: 1991. 
• 3b Masaki Y. Sakuma K. Kaji K. J. Chem. Soc., Chem. Commun.  1980,  434 
• 3c Brown HC. Basavaiah D. J. Org. Chem.  1982,  47:  5407 
• 3d Denmark SE. Amburgey J. J. Am. Chem. Soc.  1993,  115:  10386 
• 3e Amri H. Rambaud M. Villieras J. Tetrahedron  1990,  46:  3535 
• 3f Katzenellenbogen JA. Utawanit T. J. Am. Chem. Soc.  1974,  96:  6153 
• 3g Kocienski PJ. Ansell JM. Ostrow RW. J. Org. Chem.  1976,  41:  3625 
• 3h Miller JA. Zweifel G. J. Am. Chem. Soc.  1981,  103:  6217 
• 3i Coutrot P. Ghribi A. Synthesis  1986,  790 
• 3j Rossi R. Carpita A. Cossi P. Tetrahedron  1992,  48:  8801 
• 3k Basavaiah D. Krishnamacharyulu N. Hyma RS. Sarma PKS. Kumaragurabaran M. J. Org. Chem.  1999,  64:  1197 
• 4a Baylis AB, and Hillman MED. inventors; DE  2155113.  ; Chem. Abstr. 1972, 77, 34174q
• 4b Ciganek E. Org. React.  1997,  51:  201 
• 4c Basavaiah D. Rao PD. Hyma RS. Tetrahedron  1996,  52:  8001 
• 4d Basavaiah D. Rao AJ. Satyanarayana T. Chem. Rev.  2003,  103:  811 
• 5a Basavaiah D. Dharma Rao P. Suguna HR. Tetrahedron  1996,  52:  8001 
• 5b Yadav JS. Gupta MK. Pandey SK. Reddy BVS. Sarma AVS. Tetrahedron Lett.  2005,  46:  2761 
• 5c Fuocaud A. EI Guemmont F. Bull. Soc. Chim. Fr.  1989,  403 
• 5d Ko SH. Lee K.-J. J. Heterocycl. Chem.  2004,  41:  613 
• 6a Basavaiah D. Suguna HR. Muthukumara K. Kumaragurubaran N. Synthesis  2000,  217 
• 6b Roy O. Riahi A. Henin F. Muzart J. Tetrahedron  2000,  56:  8133 
• 7 Kamaimura A. Morita R. Matsuura K. Mitsudera H. Shirai M. Tetrahedron  2003,  59:  9931 
• 8 Kabalka GW. Venkataiah B. Dong G. Tetrahedron Lett.  2003,  44:  4673 
• 9 Basabaiah D. Satyanarayana T. Tetrahedron Lett.  2002,  43:  4301 
• 10a Kim JN. Chung YM. Im Y. Tetrahedron Lett.  2002,  43:  6209 
• 10b Chung YM. Lee HJ. Hwang SS. Kim JN. Bull. Korean Chem. Soc.  2001,  22:  799 
• 11 Basavaiah D. Bhavani AKD. Pandiaraju S. Sarma PKS. Synlett  1995,  243 
• 12a Basavaiah D. Sarma PKS. J. Chem. Soc., Chem. Commun.  1992,  955 
• 12b Rabe J. Hoffmann HMR. Angew. Chem., Int. Ed. Engl.  1985,  50:  3849 
• 12c Im YJ. Kim JM. Mun JH. Kim JN. Bull. Korean Chem. Soc.  2001,  22:  349 
• 13 Lee CH. Song YS. Cho HI. Yang JW. Lee K.-J. J. Heterocycl. Chem.  2003,  40:  1103 
• 14 Chandrasekhar S. Saritha B. Jagadeshwar V. Narsihmulu C. Vijay D. Sarma GD. Jagadeesh B. Tetrahedron Lett.  2006,  47:  2981 
• 15 Srihari P. Sigh AP. Jain R. Yadav JS. Synthesis  2006,  2772 
• 16 Liu YK. Xu XS. Zheng H. Xu DQ. Xu ZY. Zhang YM. Synlett  2006,  571 
• 17 Hong WP. Lee K.-J. Synthesis  2005,  33 
• 18a Basavavaiah D. Sarma PKS. Bhavani AKD. J. Chem. Soc., Chem. Commun.  1994,  1091 
• 18b Amri H. Rambaud M. Villieras J. J. Organomet. Chem.  1990,  384:  1 
• 18c Amri H. Rambaud M. Villieras JJ. Tetrahedron  1990,  46:  3535 
• 18d Song YS. Lee K.-J. J. Heterocycl. Chem.  2006,  43:  1721 
• 19 Das B. Banerjee J. Mahender G. Majhi A. Org. Lett.  2004,  6:  3349 
• 20a Liu YK. Li J. Zheng H. Xu DQ. Xu ZY. Zhang YM. Synlett  2005,  2999 
• 20b Liu YK. Zheng H. Xu DQ. Xu ZY. Zhang YM. Synlett  2006,  2492 
• 20c Liu YK. Xu DQ. Xu ZY. Zhang YM. J. Zhejiang Univ., SCIENCE B  2006,  7:  393 
• 21 Tanaka H. Kuroboshi M. Curr. Org. Chem.  2004,  8:  1027 
• According to literature reports, in the ¹H NMR spectrum of a trisubstituted alkene the β-vinylic protons, cis and trans to the ester group, are known to resonate at around δ = 7.5 and 6.5 ppm, respectively, when the alkene is substituted by an aryl group; while the same proton cis and trans to an ester group appears at around δ = 6.8 and 5.7 ppm, respectively, when substituted by an alkyl group. See:
• 22a Larson GL. de Kaifer CF. Seda R. Torres LE. Ramirez JR. J. Org. Chem.  1984,  49:  3385 
• 22b Basavaiah D. Sarma PKS. Bhavani AKD. J. Chem. Soc., Chem. Commun.  1994,  1091 
• 22c Baraldi PG. Guarneri M. Pollini GP. Simoni D. Barco A. Benetti S. J. Chem. Soc., Perkin Trans. 1  1984,  2501 
• 22d Tanaka K. Yamagishi N. Tanikaga R. Kaji A. Bull. Chem. Soc. Jpn.  1983,  56:  528 
• 23a Tanaka H. Yamashita S. Yamanoue M. Torri S. J. Org. Chem.  1989,  54:  444 
• 23b Tanaka H. Yamashita S. Katayama Y. Torri S. Chem. Lett.  1986,  2043 
• 23c Tanaka H. Yamashita S. Ikemoto Y. Torri S. Chem. Lett.  1987,  673 
• 23d Tanaka H. Yamashita S. Ikemoto Y. Torri S. Tetrahedron Lett.  1988,  29:  1721 
• 24a Falck JR. He A. Bejot R. Mioskowski C. Synlett  2006,  2652 
• 24b Baati R. Barma DK. Krishna UM. Mioskowski C. Falck JR. Tetrahedron Lett.  2002,  43:  959 

25

General Procedure for the Synthesis of 2-(2,2,2-Tri-chloroethyl)alk-2-enoates 2 In a 25 mL flask were added Al powder (0.032 g, 1.2 mmol), PbCl₂ (0.055g, 0.2 mmol), Baylis-Hillman acetate 1 (1 mmol), CCl₄ (0.20 mL, 2.0 mmol), and anhyd DMF (5 mL). The mixture was stirred at r.t. for 2-4 h. Upon completion, the solvent was removed under vacuum. Then, to the flask was added 10 mL 5% HCl for quenching the reaction, and the mixture was extracted by CH₂Cl₂ (2 × 30 mL), washed with brine (15 mL), dried over MgSO₄. After evaporation of the solvent, the residue was purified by chromatography using cyclohexane-EtOAc (6:1) as eluent to give pure 2.

26

Data for Compounds 2
Compound (E)-2a: ¹H NMR (400 MHz, CDCl₃): δ = 3.85 (s, 3 H, OCH₃), 4.17 (s, 2 H, CH₂), 7.32-7.39 (m, 5 H, ArH), 7.94 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 49.56, 52.32, 98.27, 126.66, 128.69, 128.84, 128.92, 134.88, 144.85, 168.27. IR (film): ν = 3060, 3028, 2952, 1724, 1633, 1577 cm^-1. MS (70 eV): m/z (%) = 292 [M⁺]. Anal. Calcd for C₁₂H₁₁Cl₃O₂: C, 49.09; H, 3.78. Found: C, 49.38; H, 3.74.
Compound (E)-2b: ¹H NMR (400 MHz, CDCl₃): δ = 2.37 (s, 3 H, CH₃), 3.86 (s, 3 H, OCH₃), 4.19 (s, 2 H, CH₂), 7.21 (d, 2 H, J = 8.0 Hz, ArH), 7.35 (d, 2 H, J = 8.0 Hz, ArH), 7.91 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 21.30, 49.74, 52.31, 98.48, 125.76, 129.14, 129.46, 131.97, 139.33, 144.98, 168.54. IR (film): ν = 3027, 3025, 2997, 2952, 1720, 1632, 1609 cm^-1. MS (70 eV): m/z (%) = 306 [M⁺]. Anal. Calcd for C₁₃H₁₃Cl₃O₂: C, 50.76; H, 4.26. Found: C, 50.48; H, 4.30.
Compound (E)-2c: ¹H NMR (400 MHz, CDCl₃): δ = 3.84 (s, 3 H, OCH₃), 3.86 (s, 3 H, OCH₃), 4.10 (s, 2 H, CH₂), 6.91 (d, 1 H, J = 8.0 Hz, ArH), 6.98 (t, 1 H, J = 8.0 Hz, ArH), 7.29 (d, 1 H, J = 8.0 Hz, ArH), 7.34 (t, 1 H, J = 8.0 Hz, ArH), 8.03 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 50.0, 52.28, 55.53, 98.51, 111.0, 120.54, 124.35, 126.91, 129.10, 130.36, 141.97, 157.29, 168.27. IR (film): ν = 3042, 3001, 2951, 2846, 1719, 1637, 1597 cm^-1. MS (70 eV): m/z (%) = 322 [M⁺]. Anal. Calcd for C₁₃H₁₃Cl₃O₃: C, 48.25; H, 4.05. Found: C, 48.53; H, 4.08.
Compound (E)-2d: ¹H NMR (400 MHz, CDCl₃): δ = 3.84 (s, 3 H, OCH₃), 4.17 (s, 2 H, CH₂), 6.0 (s, 2 H, OCH₂O), 6.83 (d, 1 H, J = 8.0 Hz, ArH), 6.95 (d, 1 H, J = 8.0 Hz, ArH), 6.99 (s, 1 H, ArH), 7.83 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 49.56, 52.30, 98.41, 101.44, 108.55, 108.84, 124.39, 124.90, 128.57, 144.52, 147.96, 148.39, 168.48. IR (film): ν = 3054, 3002, 2900, 1718, 1616 cm^-1. MS (70 eV): m/z (%) = 336 [M⁺]. Anal. Calcd for C₁₃H₁₁Cl₃O₄: C, 46.25; H, 3.28. Found: C, 46.52; H, 3.25
Compound (E)-2e: ¹H NMR (400 MHz, CDCl₃): δ = 3.86 (s, 3 H, OCH₃), 4.13 (s, 2 H, CH₂), 7.35 (d, 2 H, J = 8.0 Hz, ArH), 7.40 (d, 2 H, J = 8.0 Hz, ArH), 7.88 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 49.59, 52.48, 98.10, 127.33, 129.07, 130.22, 133.37, 142.13, 143.51, 168.10. IR (film): ν = 3003, 2952, 2850, 1710, 1635, 1591 cm^-1. MS (70 eV): m/z (%) = 328 [M⁺]. Anal. Calcd for C₁₂H₁₀Cl₄O₂: C, 43.94; H, 3.07. Found: C, 43.68; H, 3.11.
Compound (E)-2f: ¹H NMR (400 MHz, CDCl₃): δ = 3.88 (s, 3 H, OCH₃), 4.04 (s, 2 H, CH₂), 7.21-7.43 (m, 4 H, ArH), 7.97 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 49.41, 52.50, 97.70, 126.18, 128.43, 129.25, 129.79, 129.90, 133.87, 142.41, 167.60. IR (film): ν = 3061, 2998, 2952, 1721, 1641, 1590 cm^-1. MS (70 eV): m/z (%) = 328 [M⁺]. Anal. Calcd for C₁₂H₁₀Cl₄O₂: C, 43.94; H, 3.07. Found: C, 43.75; H, 3.04.
Compound (E)-2g: ¹H NMR (400 MHz, CDCl₃): δ = 3.88 (s, 3 H, OCH₃), 4.01 (s, 2 H, CH₂), 7.24 (d, 1 H, J = 8.0 Hz, ArH), 7.29 (d, 1 H, J = 8.0 Hz, ArH), 7.45 (s, 1 H, ArH), 7.89 (s, 1 H, ArCH=). ¹³C NMR (100 MHz, CDCl₃): δ = 49.34, 52.54, 97.49, 127.25, 128.98, 129.70, 130.0, 132.37, 134.59, 135.12, 140.07, 141.12, 166.50. IR (film): ν = 3092, 3001, 2954, 1729, 1643, 1586 cm^-1. MS (70 eV): m/z (%) = 362 [M⁺]. Anal. Calcd for C₁₂H₉Cl₅O₂: C, 39.76; H, 2.50. Found: C, 39.51; H, 2.53.
Compound (E)-2h: ¹H NMR (400 MHz, CDCl₃): δ = 3.90 (s, 3 H, OCH₃), 4.13 (s, 2 H, CH₂), 7.64 (t, 1 H, J = 8.0 Hz, ArH), 7.75 (d, 1 H, J = 8.0 Hz, ArH), 7.97 (s, 1 H), 8.22 (d, 1 H, J = 8.0 Hz, ArH), 8.27 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 49.26, 52.61, 97.62, 123.37, 129.15, 129.84, 134.41, 136.54, 140.81, 141.90, 148.22, 167.45. IR (film): ν = 3086, 2954, 1725, 1639, 1532 cm^-1. MS (70 eV):
m/z (%) = 337 [M⁺]. Anal. Calcd for C₁₂H₁₀Cl₃NO₂: C, 42.57; H, 2.98. Found: C, 42.33; H, 2.95.
Compound (E)-2i: ¹H NMR (400 MHz, CDCl₃): δ = 3.83 (s, 3 H, OCH₃), 4.39 (s, 2 H, CH₂), 6.51 (d, 1 H, J = 1.2 Hz, ArH), 6.74 (dd, 1 H, J ₁ = 4.0 Hz, J ₂ = 1.2 Hz, ArH), 7.42 (s, 1 H, ArCH=), 7.59 (d, 1 H, J = 4.0 Hz, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 50.44, 52.30, 98.64, 112.16, 118.54, 121.02, 130.39, 145.17, 150.41, 168.35. IR (film): ν = 2952, 1717, 1636 cm^-1. MS (70 eV): m/z (%) = 282 [M⁺]. Anal. Calcd for C₁₀H₉Cl₃O₃: C, 42.36; H, 3.20. Found: C, 42.58; H, 3.25.
Compound (E)-2j: ¹H NMR (400 MHz, CDCl₃): δ = 2.68 (q, 2 H, J = 8.0 Hz, CH₂), 2.78 (t, 2 H, J = 8.0 Hz, CH₂), 3.77 (s, 3 H, OCH₃), 3.78 (s, 2 H, CH₂), 7.09 (t, 1 H, J = 8.0 Hz, CH=), 7.16-7.31 (m, 5 H, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 31.88, 34.44, 50.07, 52.11, 98.68, 126.27, 128.24, 128.36, 128.51, 140.42, 148.00, 167.73. IR (film): ν = 3063, 3028, 2950, 1723, 1646, 1603 cm^-1. MS (70 eV): m/z (%) = 320 [M⁺]. Anal. Calcd for C₁₄H₁₅Cl₃O₂: C, 52.28; H, 4.70. Found: C, 52.54; H, 4.64.
Compound (E)-2k: ¹H NMR (400 MHz, CDCl₃): δ = 0.88 (t, 3 H, J = 6.8 Hz, CH₃), 1.27-1.33 (m, 10 H), 2.37 (q, 2 H, J = 8.0 Hz, CH₂), 3.78 (s, 3 H, OCH₃), 3.85 (s, 2 H, CH₂), 7.06 (t, 1 H, J = 8.0 Hz, CH=). ¹³C NMR (100 MHz, CDCl₃): δ = 13.99, 22.55, 28.41, 29.01, 29.29, 30.08, 31.65, 50.20, 52.02, 98.88, 125.71, 149.75, 167.92. IR (film): ν = 2927, 2856, 1724, 1646 cm^-1. MS (70 eV): m/z (%) = 314 [M⁺]. Anal. Calcd for C₁₃H₂₁Cl₃O₂: C, 49.46; H, 6.71. Found: C, 49.28; H, 6.66.