Synlett 2019; 30(12): 1437-1441
DOI: 10.1055/s-0039-1690096
letter
© Georg Thieme Verlag Stuttgart · New York

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

Xu yan Cao
,
Fei Huang
,
Songlin Zhang
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou, 215123, P. R. of China   Email: zhangsl@suda.edu.cn
› Author Affiliations
The study was supported by the Project of Scientific and Technologic Infrastructure of Suzhou (No. SZS201207) and by the National Natural Science Foundation of China (No. 21072143). We gratefully acknowledge the Priority Academic Program Development of Jiangsu Higher Education Institutions for funding the project.
Further Information

Publication History

Received: 25 March 2019

Accepted after revision: 20 May 2019

Publication Date:
25 June 2019 (eFirst)

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.

Supporting Information

 
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  • 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.