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DOI: 10.1055/s-2003-42069
The Room-Temperature Palladium-Catalyzed Cyanation of Aryl Bromides and Iodides with Tri-t-butylphosphine as Ligand
Publikationsverlauf
Publikationsdatum:
07. Oktober 2003 (online)
Abstract
The palladium-catalyzed cyanation of aryl bromides and iodides to the corresponding nitriles occurs at room temperature when tri-t-butylphosphine is used as ligand, Zn(CN)2 as the cyanide source and Zn dust as a co-catalyst in DMF as solvent. A variety of aromatic halides, including electron-withdrawing and electron-donating, can be efficiently cyanated under these conditions. The reactions are completed in less than 1 hour and products are produced in good to excellent yield.
Key words
palladium-catalyzed - cyanation - aryl iodide - aryl bromide - tri-t-butylphosphine.
- 1
Larock RC. Comprehensive Organic Transformations, A Guide to Functional Group Preparations VCH Publishers; New York: 1989. - For recent examples:
-
2a
Zhang A.Neumeyer JL. Org. Lett. 2003, 5: 201 -
2b
Sundermeier M.Zapf A.Beller M.Sans J. Tetrahedron Lett. 2001, 42: 6707 -
2c
Jin F.Confalone PN. Tetrahedron Lett. 2000, 41: 3271 -
2d
Alterman M.Hallberg A. J. Org. Chem. 2000, 65: 7984 -
2e
Maligres PE.Waters MS.Fleitz F.Askin D. Tetrahedron Lett. 1999, 40: 8193 -
2f
Anderson BA.Bell EC.Ginah FO.Harn NK.Pagh LM.Wepseic JP. J. Org. Chem. 1998, 63: 8224 -
2g
Kubota H.Rice KC. Tetrahedron Lett. 1998, 39: 2907 -
2h
Sakaikibara Y.Ido Y.Sasaki K.Sakai M.Uchino N. Bull. Chem. Soc. Jpn. 1993, 66: 2776 -
3a
Littke AF.Dai C.Fu GC. J. Am. Chem. Soc. 2000, 122: 4020 -
3b
Littke AF.Fu GC. Angew. Chem. Int. Ed. 1998, 37: 3387 -
4a
Littke AF.Fu GC. J. Am. Chem. Soc. 2001, 123: 6989 -
4b
Littke AF.Fu GC. J. Org. Chem. 1999, 64: 10 - 5
Dai C.Fu GC. J. Am. Chem. Soc. 2001, 123: 2719 - 6
Hundertmark T.Littke AF.Buchwald SL.Fu GC. Org. Lett. 2000, 2: 1729 - 7
Hartwig JF.Kawatsura Hauck SI.Shaughnessy KH.Alcazar-Roman LM. J. Org. Chem. 1999, 64: 5575 - 8
Littke AF.Schwarz L.Fu GC. J. Am. Chem. Soc. 2002, 124: 6343 - 9
Ueda M.Miyaura N. J. Org. Chem. 2000, 65: 4450 - 10
Okkano T.Iwahara M.Kiji J. Synlett 1998, 243
References
General Procedure: An oven-dried, Ar-purged, round bottom flask was charged with the aryl halide (0.5 mmol), Zn(CN)2 (0.9 mmol), Pd2(dba)3 (0.013 mmol), and Zn dust (0.06 mmol) followed by DMF (5 mL). The ligand (10 wt% in hexane, 0.025 mmol) was added and the reaction mixture was rapidly stirred at r.t. for 1 h. After this time, the mixture was partitioned between 20 mL EtOAc and 10 mL H2O. The EtOAc layer was separated, washed with brine (10 mL) and dried over MgSO4. After concentration, the residue was subjected to silica gel column chromatography using a hexane-EtOAC solvent system to furnish the aryl nitrile. Spectroscopic data and melting points were consistent with known values.