PDF herunterladen
Synlett 2007(4): 0543-0546  
DOI: 10.1055/s-2007-970741
LETTER
© Georg Thieme Verlag Stuttgart · New York

Cyanation of Aryl Chlorides with Potassium Hexacyanoferrate(II) Catalyzed by Cyclopalladated Ferrocenylimine Tricyclohexylphosphine Complexes

Yi-nan Cheng, Zheng Duan*, Ting Li, Yangjie Wu*
Chemistry Department, the Key Lab of Chemical Biology and Organic Chemistry of Henan Province, the Key and Open Lab of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou 450052, P. R. of China
Fax: +86(371)67979408; e-Mail: duanzheng@zzu.edu.cn; e-Mail: wyj@zzu.edu.cn;
Weitere Informationen

Publikationsverlauf

Received 9 October 2006
Publikationsdatum:
21. Februar 2007 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Cyanation of aryl chlorides with potassium hexacyano­ferrate(II) catalyzed by cyclopalladated ferrocenylimine tricyclohexylphosphine complex has been described. This method is applicable to both activated and deactivated aryl chlorides. The ­corresponding aryl nitriles were isolated in good to excellent yields

Key words

cyclopalladium - cyanation - aryl chloride - catalysis - coupling

19

General Procedure.
A reaction vessel was charged with 1 mmol Na2CO3, 0.22 mmol K4[Fe(CN)6]·3H2O and 2% mol catalyst 2a. The vessel was then evacuated and backfilled with N2 four times. Then, 1 mmol aryl chloride in 1 mL NMP was added to the vessel. The mixture was heated at 140 °C for 16-24 h. The suspension was cooled down to r.t., diluted with 5 mL CH2Cl2 and washed with 5 mL H2O. The aqueous layer was extracted twice with CH2Cl2 (3 mL) and the combined organic layers were dried over MgSO4. After evaporation of the solvents the residue was subjected to TLC (hexane-EtOAc). All prepared compounds were known and identified by 1H NMR, 13C NMR and MS.
Selected Data.
Compound 4c: 1H NMR (400 MHz, CDCl3): δ = 2.53 (s, 6 H), 7.11 (d, J = 7.7 Hz, 2 H), 7.34 (dd, J = 7.7 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.8, 113.3, 117.3, 127.3, 132.1, 142.1 ppm. MS (ESI): m/z = 154.1 [M + Na]+.
Compound 4e: 1H NMR (400 MHz, CDCl3): δ = 3.87 (s, 3 H), 6.95 (d, J = 8.9 Hz, 2 H), 7.58 (d, J = 8.9 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.3, 103.7, 114.5, 119.0, 133.7, 162.6 ppm. MS (ESI): m/z = 156.0 [M + Na]+.
Compound 4i: 1H NMR (400 MHz, CDCl3): δ = 1.42 (t, J = 7.2 Hz, 3 H), 4.42 (q, J = 7.1 Hz, 2 H), 7.74 (d, J = 8.3 Hz, 2 H), 8.14 (d, J = 8.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.0, 61.6, 116.0, 117.8, 129.8, 131.9, 134.1, 164.7 ppm. MS (ESI): m/z = 197.8 [M + Na]+.
Compound 4j: 1H NMR (400 MHz, CDCl3): δ = 7.45 (m, 1 H), 7.98 (m, 1 H), 8.83 (m, 1 H), 8.91 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 110.3, 116.5, 123.6, 139.3, 152.5, 153.0 ppm. MS (ESI): m/z = 105.0 [M + H]+.