An Example of Ketone Olefination via Praseodymium-Mediated Barbier Reaction in the Presence of Diethyl Phosphite

Abstract

The first example of carbon double-bond formation via praseodymium-mediated Barbier type reaction of ketones and allyl halides in the presence of diethyl phosphite is reported. The reaction is highly α-regioselective and conveniently carried out under mild conditions in a one-pot fashion. From a synthetic point of view, a series of conjugated alkenes were obtained in moderate to good yields in this one-pot reaction with practical reaction conditions.

Key words

Barbier type reaction - ketones - diethyl phosphite - α-regioselective - conjugated alkenes

• References and Notes

• 1a Nicolaou KC, Ramphal JY, Petasis NA, Serhan CN. Angew. Chem. Int. Ed. Engl. 1991; 30: 1100 ; Angew. Chem. 1991, 103, 1119
• 1b Sandri J, Viala J. J. Org. Chem. 1995; 60: 6627
• 1c Lucet D, Gall TL, Mioskowski C. Angew. Chem. Int. Ed. 1998; 37: 2580 ; Angew. Chem. 1998, 110, 2724
• 1d Kotti SR. S. S, Timmons C, Li G.-G. Chem. Biol. Drug Des. 2006; 67: 101
• 1e Takao K, Munakata R, Tadano K. Chem. Rev. 2005; 105: 4779
• 1f Alvarez R, Vaz B, Gronemeyer H, deLera AR. Chem. Rev. 2014; 114: 1-125
• 2a Wittig G, Geissler G. Justus Liebigs Ann. Chem. 1953; 580: 44
• 2b Wittig G, Schollkopf U. Chem. Ber. 1954; 97: 1318
• 2c Wittig G, Schlosser M. Tetrahedron 1962; 18: 1023
• 2d Maryanoff BE, Reitz AB. Chem. Rev. 1989; 89: 863
• 3a Lee GH, Lee HK, Choi EB, Kim BT, Pak CS. Tetrahedron Lett. 1995; 36: 5607
• 3b Pospisil J, Pospisil T, Marko IE. Org. Lett. 2005; 7: 2373
• 4a Ager DJ. Org. React. 1990; 38: 1-223
• 4b Staden LF, Gravestock D, Ager DJ. Chem. Soc. Rev. 2002; 31: 195
• 5 Lakhrissi M, Chapleur Y. Angew. Chem. Int. Ed. Engl. 1996; 35: 750
• 6 Wong KT, Hung YY. Tetrahedron Lett. 2003; 44: 8033
• 7 Hopf H, Hänel R, Trætteberg M, Bakken P. Eur. J. Org. Chem. 1998; 467
• 8 Dennis KP. N, Luh TY. J. Am. Chem. Soc. 1989; 11: 9119
• 9a Mitsudo T, Kadokura M, Watanabe Y. J. Org. Chem. 1987; 52: 1695
• 9b Negishi EI, Huang Z.-H, Wang G.-W, Mohan S, Wang C, Hattori H. Acc. Chem. Res. 2008; 41: 1474
• 10 Murelli RP, Snapper ML. Org. Lett. 2007; 9: 1749
• 11a Li Y, Hu Y.-Y, Zhang S.-L. Chem. Commun. 2013; 49: 10635
• 11b Hu Y.-Y, Zhao T, Zhang S.-L. Chem. Eur. J. 2010; 16: 1697
• 12a Wang T.-Q, Hu Y.-Y, Zhang S.-L. Org. Biomol. Chem. 2010; 8: 2312
• 12b Qi W.-K, Wang P.-P, Fan L.-Y, Zhang S.-L. J. Org. Chem. 2013; 78: 5918
• 13 Cui H, Li Y, Zhang S.-L. Org. Biomol. Chem. 2012; 10: 2862
• 14a Li J.-L, Hu D.-C, Liang X.-P, Wang Y.-C, Wang H.-S, Pan Y.-M. J. Org. Chem. 2017; 82: 9006
• 14b Xie Y.-Y, Wang Y.-C, Qu H.-E, Tan X.-C, Wang H.-S, Pan Y.-M. Adv. Synth. Catal. 2014; 356: 3347
• 14c Wang Y, Li J, He Y, Xie Y, Wang H, Pan Y. Adv. Synth. Catal. 2015; 357: 3229
• 14d Wang Y.-C, Xie Y.-Y, Qu H.-E, Wang H.-S, Pan Y.-M, Huang F.-P. J. Org. Chem. 2014; 79: 4463
• 14e Wang X, Li S.-Y, Pan Y.-M, Wang H.-S, Liang H, Chen Z.-F, Qin X.-H. Org. Lett. 2014; 16: 580
• 15 Wu S, Li Y, Zhang S.-L. J. Org. Chem. 2016; 81: 8070
• 16 General Procedure for Synthesis of Dienes (2aa–af) To a suspension of carbonyl compound (0.5 mmol) and praseodymium (1.5 mmol) in THF (3 mL) was added halide (2 mmol) and catalytic amounts of I₂ under a nitrogen atmosphere at room temperature. The mixture was stirred for 2 h, then diethyl phosphite (0.6 mmol) was added and the mixture was stirred at 65 °C for 12 h. The reaction was then quenched with dilute hydrochloric acid and the resulting mixture was extracted with diethyl ether (3 × 10 mL), and dried over anhydrous Na₂SO₄. The solvent was removed by evaporation under reduced pressure. Purification by column chromatography on silica gel afforded olefins (300–400 mesh, petroleum ether as eluent). Buta-1,3-diene-1,1-diyldibenzene (2aa) Yield: 91.7 mg (89%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.25 (m, 8 H), 7.23–7.20 (m, 2 H), 6.71 (d, J = 11.0 Hz, 1 H), 6.44 (dt, J = 16.9, 10.5 Hz, 1 H), 5.42–5.36 (m, 1 H), 5.15–5.10 (m, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.26, 142.21, 139.77, 135.08, 130.54, 128.64, 128.32, 128.29, 127.71, 127.63, 127.52, 118.73. HRMS (EI⁺): m/z [M⁺] calcd for C₁₆H₁₄: 206.1096; found: 206.1089. Methyl-4-(4-methyl-1-phenylpenta-1,3-dien-1-yl)benzene (2fc) Yield: 96.7 mg (78%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.37–7.29 (m, 1 H), 7.26–7.04 (m, 8 H), 6.84 (d, J = 11.4 Hz, 1 H), 5.93 (dd, J = 18.3, 11.5 Hz, 1 H), 2.34 (d, J = 25.6 Hz, 3 H), 1.87 (s, 3 H), 1.74 (d, J = 4.2 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 140.49, 140.44, 139.87, 139.78, 137.44, 137.23, 136.79, 130.69, 130.61, 128.98, 128.93, 128.20, 128.18, 127.62, 127.46, 127.07, 126.97, 124.45, 123.86, 123.47, 123.36, 26.59, 21.39, 21.21, 18.74, 18.72. HRMS (EI⁺): m/z [M⁺] calcd for C₁₉H₂₀: 248.3490; found: 248.3484. [1,1′-Biphenyl]-4-yl(phenyl)methanone (2gd) Yield: 136.4 mg (88%); colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.65–7.54 (m, 3 H), 7.52–7.27 (m, 10 H), 7.21 (dd, J = 13.9, 6.7 Hz, 1 H), 6.91 (dd, J = 23.6, 11.4 Hz, 1 H), 5.98 (dd, J = 33.3, 11.4 Hz, 1 H), 1.89 (s, 3 H), 1.76 (d, J = 6.4 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 142.13, 140.87, 139.75, 139.39, 139.36, 137.98, 137.95, 131.19, 130.72, 128.90, 128.87, 128.29, 127.88, 127.71, 127.38, 127.30, 127.21, 127.13, 127.03, 126.95, 126.88, 124.88, 124.59, 123.39, 26.64, 18.79. HRMS (EI⁺): m/z [M⁺] calcd for C₂₄H₂₂: 310.4400; found: 310.4421. (3-Methylbuta-1,3-diene-1,1-diyl)dibenzene (2ae) Yield: 58.3 mg (53%); white oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.25 (q, J = 5.7 Hz, 3 H), 7.19–7.04 (m, 9 H), 6.58 (s, 1 H), 4.91 (d, J = 13.5 Hz, 2 H), 1.40 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.43, 142.56, 141.64, 140.78, 130.87, 130.46, 128.22, 128.06, 127.60, 127.35, 119.24, 22.20. HRMS (EI⁺): m/z [M⁺] calcd for C₁₇H₁₆: 220.3150; found: 220.3135.