Efficient Solvent-Free Synthesis of Homoallylic Alcohols Mediated by Zinc-Copper Couple

Abstract

Under solvent-free conditions, it was found that zinc-copper couple could efficiently mediate the Barbier-type reaction of ketones and allyl bromide to give the corresponding homoallylic alcohols in high to excellent yields at room temperature.

solvent-free - zinc-copper couple - ketones - allylation - homoallylic alcohols

References and Notes

1a Romo D. Meyer SD. Johnson DD. Schreiber SL. J. Am. Chem. Soc.  1993,  115:  9345 

1b Nicolaou KC. Kim DW. Baati R. Angew. Chem. Int. Ed.  2002,  41:  3701 

2 Yamamoto Y. Asao N. Chem. Rev.  1993,  93:  2207 

3a Li CJ. Chem. Rev.  1993,  93:  2023 

3b Lubineau A. Auge J. Queneau Y. Synthesis  1994,  741 

3c Tan XH. Shen B. Liu L. Guo QX. Tetrahedron Lett.  2002,  43:  9373 

4a Anastas PT. Warner JC. Green Chemistry: Theory and Practice   Oxford University Press; New York: 1997. 

4b Li CJ. Chan TH. Organic Reactions in Aqueous Media   John Wiley & Sons; New York: 1997. 

5a Chan TH. Li CJ. Lee MC. Wei ZY. Can. J. Chem.  1994,  72:  1181 

5b Cintas P. Synlett  1995,  1087 

5c Chan TH. Yang Y. J. Am. Chem. Soc.  1999,  121:  3228 

5d Loh TP. Zhou JR. Yin Z. Org. Lett.  1999,  1:  1855 

5e Hilt G. Smolko KI. Waloch C. Tetrahedron Lett.  2002,  43:  1437 

5f Augé J. Lubin-Germain N. Marque S. Seghrouchn L. J. Organomet. Chem.  2003,  679:  79 

6a Li LH. Chan TH. Tetrahedron Lett.  2000,  41:  5009 

6b Wang W. Shi L. Huang Y. Tetrahedron  1990,  46:  3315 

7 Zhou JY. Jia Y. Sun GF. Wu SH. Synth. Commun.  1997,  27:  899 

8a Li CJ. Meng Y. Yi XH. Ma JH. Chan TH. J. Org. Chem.  1998,  63:  7498 

8b Ren PD. Pan SF. Dong TW. Wu SH. Chin. J. Chem.  1996,  14:  462 

9 Chan TC. Lau CP. Chan TH. Tetrahedron Lett.  2004,  45:  4189 

10 Zhang WC. Li CJ. J. Org. Chem.  1999,  64:  3230 

11a Wang J.-X. Jia XF. Meng TJ. Xin L. Synthesis  2005,  2838 

11b Marton D. Stivanello D. Tagliavini G. J. Org. Chem.  1996,  61:  2731 

11c Yi XH. Haberman JX. Li CJ. Synth. Commun.  1998,  28:  2999 

11d Zhou CL. Zhou YQ. Jiang JY. Tetrahedron Lett.  2004,  45:  5537 

12a Mukaiyama T. Harada T. Chem. Lett.  1981,  10:  1527 

12b Wang ZY. Zha ZG. Zhou CL. Org. Lett.  2002,  4:  1683 

12c Chan TH. Yang Y. Li CJ. J. Org. Chem.  1999,  64:  4452 

12d Tan XH. Hou YQ. Huang C. Liu L. Guo QX. Tetrahedron  2004,  60:  6129 

12e Tang L. Ding L. Chang WX. Li J. Tetrahedron Lett.  2006,  47:  303 

12f Wang J. Yuan G. Dong C.-Q. Chem. Lett.  2004,  33:  286 

12g Andrews PC. Peatt AC. Raston CL. Tetrahedron Lett.  2002,  43:  7541 

13a Wang ZY. Yuan SZ. Zha ZG. Zhang ZD. Chin. J. Chem.  2003,  21:  1231 

13b Andrews PC. Peatt AC. Raston CL. Tetrahedron Lett.  2004,  45:  243 

13c Wang ZY. Yuan SZ. Li CJ. Tetrahedron Lett.  2002,  43:  5097 

14 Chan TH. Yang Y. Tetrahedron Lett.  1999,  40:  3863 

15 Loh TP. Xu J. Tetrahedron Lett.  1999,  40:  2431 

16a Tanaka K. Solvent-Free Organic Synthesis   Wiley-VCH; Weinheim: 2003. 

16b Astruc D. Heuzé K. Gatard S. Méry D. Nlate S. Plault L. Adv. Synth. Catal.  2005,  347:  329 

16c Cave GWV. Raston CL. Scott JL. Chem. Commun.  2001,  2159 

16d Mestres R. Green Chem.  2004,  6:  853 

16e Cole-Hamilton DJ. Science  2003,  299:  1072 

17 Hamasaki R. Chounan Y. Horino H. Yamamoto Y. Tetrahedron Lett.  2000,  41:  9883 

18a Wang J.-X. Fu Y. Hu YL. Angew. Chem. Int. Ed.  2002,  41:  2757 

18b Wang J.-X. Fu Y. Hu YL. Wang KH. Synthesis  2003,  1506 

18c Hu YL. Wang J.-X. Li WB. Chem. Lett.  2001,  30:  174 

18d Wang J.-X. Wang KH. Zhao LB. Li HX. Fu Y. Hu YL. Adv. Synth. Catal.  2006,  348:  1262 

18e Huang DF. Wang J.-X. Synlett  2007,  2272 

19a Hennion GF. Sheehan JJ. J. Am. Chem. Soc.  1949,  71:  1964 

19b Shank RS. Shechter H. J. Org. Chem.  1959,  24:  1825 

19c LeGoff E. J. Org. Chem.  1964,  29:  2048 

19d Suarez RM. Sestelo JP. Sarandeses LA. Synlett  2002,  1435 

19e Shimizu M. Iwata A. Makino H. Synlett  2002,  1538 

19f Estevam IHS. Bieber LW. Tetrahedron Lett.  2003,  44:  667 

20

Preparation of the Zinc-Copper Couple: Zinc powder (11.6 g) and distilled H₂O (80 mL) were placed into a 100-mL round-bottom flask equipped with a stir bar. With stirring, HCl acid (37%, 2 × 1 mL) was added over 10 min. Then the CuSO₄ solution (20%, 20 mL) was added dropwise with stirring and the stirring was continued for about 15 min. Finally, the mixture was filtered and the solid was washed with H₂O (3 × 30 mL), acetone (3 × 10 mL), and Et₂O (2 × 10 mL). Then the solid was transferred into a flask equipped with vacuum take-off and dried under vacuum for 3 h at 100 °C. Other M-Cu couples were also prepared in this way.Preparation of the Homoallylic Alcohols: Zinc-copper couple (0.24 g), allyl bromide (2.5 mmol) and ketones (2 mmol) were placed in a dried round-bottom flask, and the mixture was stirred at r.t. and the reaction was monitored by TLC. After reaction completed, sat. brine (10 mL) was poured into the mixture, the mixture was extracted with Et₂O (3 × 10 mL) and the organic layer was separated, dried over anhyd MgSO₄, filtered, and evaporated. The pure products were obtained by flash chromatography over silica gel, and characterized by IR, ¹H NMR, ¹³C NMR and MS.

21

Representative Spectroscopic Data for Compounds 3. Compound 3i: IR: 3475, 2976, 1670, 1456, 1269, 1101, 920, 771, 738 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 7.24-7.84 (m, 7 H), 5.60-5.70 (m, 1 H), 5.09-5.19 (m, 2 H), 3.88 (q, J = 6.4 Hz, 2 H), 2.65-2.76 (m, 1 H), 2.52-2.63 (m, 1 H), 2.14 (s, 1 H), 1.61 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 146.4, 143.3, 143.3, 141.4, 140.2, 133.7, 126.7, 126.5, 125.0, 123.4, 121.5, 119.8, 119.4, 73.8, 48.6, 37.0, 30.1, 26.8. EI-MS: m/z (%) = 250 (2.4) [M⁺], 209 (64.9), 193 (16.8), 165 (37.7), 43 (100), 39 (17.2). Anal. Calcd for C₁₈H₁₈O: C, 86.36; H, 7.25. Found: C, 86.36; H, 7.36. Compound 3p: IR: 3406, 3077, 2977, 1644, 1439, 1372, 1114, 923, 796 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.88 (d, J = 3.6 Hz, 1 H), 6.63 (d, J = 3.6 Hz, 1 H), 5.67-5.78 (m, 1 H), 5.12-5.19 (m, 2 H), 2.57-2.67 (m, 1 H), 2.48-2.54 (m, 1 H), 2.34 (s, 1 H), 1.57 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 154.6, 132.8, 129.5, 122.5, 120.2, 110.5, 73.0, 48.7, 30.1. EI-MS: m/z (%) = 248 (0.3) [M⁺ + 2], 246 (0.2) [M⁺], 231 (0.3) [M⁺ - Me], 229 (0.3) [M⁺ - OH], 207 (33.7), 43 (100), 39 (21.7). Anal. Calcd for C₉H₁₁BrOS: C, 43.74; H, 4.49. Found: C, 43.29; H, 3.93. Compound 3q: IR: 3439, 3072, 2922, 1662, 1445, 1369, 1142, 917, 829 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.54 (s, 1 H), 5.67-5.78 (m, 1 H), 5.12-5.17 (m, 2 H), 2.15-2.50 (m, 8 H), 2.04 (s, 1 H), 1.51 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 142.1, 134.2, 133.9, 131.3, 125.3, 119.2, 73.6, 47.7, 30.9, 29.3, 15.0. EI-MS: m/z (%) = 196 (2.37) [M⁺], 181 (0.04) [M⁺ - OH], 155 (24.9), 139 (10.5), 113 (5.7), 59 (9.3), 43 (100), 41 (16.2), 39 (16.9). Anal. Calcd for C₁₁H₁₆OS: C, 67.30; H, 8.22. Found: C, 66.92; H, 8.07. Compound 3r: IR: 3411, 3077, 2981, 1684, 1373, 1097, 921, 786 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 6.05 (s, 1 H), 5.87 (s, 1 H), 5.68-5.72 (m, 1 H), 5.11-5.15 (m, 2 H), 2.64-2.69 (m, 1 H), 2.51-2.56 (m, 1 H), 2.28 (s, 3 H), 2.14 (s, 1 H), 1.51 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 157.3, 151.2, 133.5, 119.0, 105.8, 105.3, 70.5, 46.0, 26.3, 13.5. EI-MS: m/z (%) = 166 (0.7) [M⁺], 149 (1.7) [M⁺ - OH], 135 (0.7), 125 (91.5), 109 (10.3), 95 (2.1), 43 (100), 39 (20.6). Anal. Calcd for C₁₀H₁₄O₂: C, 72.26; H, 8.49. Found: C, 72.28; H, 8.64.