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

Yunkui Liu; Danqian Xu; Zhenyuan Xu; Yongmin Zhang

doi:10.1055/s-2007-984507

LETTER

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

Yunkui Liu^a, Danqian Xu^a, Zhenyuan Xu*^a, Yongmin Zhang*^b,c
^a State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
^b Department of Chemistry, Zhejiang University, Xi-xi Campus, Hangzhou 310028, P. R. of China
Fax: +86(571)88320066; e-Mail: greensyn@zjut.edu.cn;
^c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

Abstract

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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

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References

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.