Conjugate Hydrocyanation of Aromatic Enones Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source

Zheng Li; Chenhui Liu; Yupeng Zhang; Rongzhi Li; Ben Ma; Jingya Yang

doi:10.1055/s-0032-1317179

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(17): 2567-2571
DOI: 10.1055/s-0032-1317179

letter

Conjugate Hydrocyanation of Aromatic Enones Using Potassium Hexacyanoferrate(II) as an Eco-Friendly Cyanide Source

Autoren

Zheng Li*

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn
Chenhui Liu

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn
Yupeng Zhang

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn
Rongzhi Li

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn
Ben Ma

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn
Jingya Yang

College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, P. R. of China Fax: +86(931)7971989 eMail: lizheng@nwnu.edu.cn

Abstract

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Abstract

A selective conjugate hydrocyanation of aromatic enones by a one-pot, two-step procedure using potassium hexacyanoferrate(II) as an original eco-friendly cyanide source, potassium hydroxide as a base, and benzoyl chloride as a promoter was described. This protocol has the advantages of a nontoxic cyanide source, high yield, and simple workup procedure.

Key words

conjugate hydrocyanation - 1,4-addition - aromatic enone - green chemistry - nucleophilic addition - potassium hexacyanoferrate(II)

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Referenzen

References and Notes

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12 The analytical data for the isolated representative acyl cyanides are given below. Benzoyl Cyanide White solid. IR (KBr): 2224 (CN), 1679 (C=O) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 8.15–8.13 (m, 2 H), 7.82–7.78 (m, 1 H), 7.63–7.59 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 167.8, 136.8, 133.2, 130.4, 129.5, 112.6.
13 General Procedure The mixture of K₄[Fe(CN)₆] (0.4 mmol) and benzoyl chloride (2 mmol) was heated at 160 °C for 3 h, then the reaction system was cooled to 40 °C, and aromatic enone (1.5 mmol) in MeCN (5 mL) and KOH (2.4 mmol) in H₂O (3 mL) were added. The mixture was further stirred at 40 °C for the appropriate time indicated in Table 4. After completion of the reaction, monitored by TLC, the resulting mixture was filtered to remove the solids, and the filtrate was concentrated and isolated by column chromatography using PE–EtOAc (10:1) as eluent to give the pure product. The analytical data for representative products are shown below. 4-Oxo-2,4-diphenylbutanenitrile (Table 4, Entry 1) White solid; mp 120–122 °C. IR (KBr): 1681 (C=O), 2238 (CN) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.51 (dd, 1 H, J = 5.6, 18.0 Hz, CHCH _aHCO), 3.74 (dd, 1 H, J = 7.6, 18.0 Hz, CHCH _bHCO), 4.58 (dd, J = 6.0, 6.4 Hz, 1 H, ArCHCH₂), 7.26–7.43 (m, 7 H, ArH), 7.58–7.62 (m, 1 H, ArH), 7.92–7.94 (m, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 31.9, 44.5, 120.6, 127.5, 128.1, 128.4, 128.8, 129.3, 133.9, 135.2, 135.6 194.6 ppm. Anal. Calcd for C₁₆H₁₃NO (235.28): C, 81.68; H, 5.57; N, 5.95. Found: C, 81.59; H, 5.56; N, 5.97. 4-(4-Methoxyphenyl)-4-oxo-2-phenylbutanenitrile (Table 4, Entry 3) Oil. IR (KBr): 1676 (C=O), 2243 (CN) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.37 (dd, J = 6.0, 17.6 Hz, 1 H, CHCH _aHCO), 3.60 (dd, J = 8.4, 17.6 Hz, 1 H, CHCH _bHCO), 3.79 (s, 3 H, CH₃), 4.49 (dd, J = 6.0, 8.0 Hz, 1 H, ArCHCH₂), 6.85 (d, J = 6.8 Hz, 2 H, ArH), 7.23–7.37 (m, 5 H, ArH), 7.83 (d, J = 6.8 Hz, 2 H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 31.9, 44.1, 55.5, 113.9, 120.8, 127.4, 128.3, 128.7, 129.2, 130.4, 135.4, 164.0, 193.0 ppm. Anal. Calcd for C₁₇H₁₅NO₂ (265.31): C, 76.96; H, 5.70; N, 5.28. Found: C, 76.80; H, 5.71; N, 5.30.

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