Categories: C-C Bond Formation > Nitrogen-containing molecules >
Synthesis of Nitriles
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Recent Literature
A solvent-free [Cp*IrCl2]2-catalyzed reaction of substituted acetonitriles with primary alcohols delivered monosubstituted aryl/heteroaryl acetonitriles in excellent yield. This process can be achieved by conventional or microwave heating.
C. Löfberg, R. Grigg, M. A. Whittaker, A. Keep, A. Derrick, J. Org. Chem., 2006,
71, 8023-8027.
A one-pot protocol for the cyanomethylation of aryl halides through a
palladium-catalyzed reaction with isoxazole-4-boronic acid pinacol ester
proceeds through Suzuki coupling, base-induced fragmentation, and deformylation.
Under optimized conditions (PdCl2dppf, KF, DMSO/H2O, 130
°C) a broad spectrum of aryl bromides could be converted into arylacetonitriles
in good yields.
J. Velcicky, A. Soicke, R. Steiner, H.-G. Schmalz, J. Am. Chem. Soc., 2011,
133, 6948-6951.
A palladium-catalyzed α-arylation of nitriles was developed by exploring the structure and reactivity of arylpalladium cyanoalkyl complexes. The high yields and short reaction times observed for BINAP-ligated complexes suggested that BINAP-ligated palladium catalysts might be appropriate for the arylation of nitriles. Initial results on a palladium-catalyzed process for the direct coupling of aryl bromides and primary, benzylic, and secondary nitrile anions to form α-aryl nitriles in good yields are reported.
D. A. Culkin, J. F. Hartwig, J. Am. Chem. Soc., 2002,
124, 9330-9331.
TMPZnCl·LiCl as a kinetically highly active base enables a Pd-catalyzed
α-arylation of nitriles and esters under mild conditions. Remarkably, even a
regioselective γ-arylation or a γ-alkenylation of α,β- or β,γ-unsaturated
nitriles can be observed.
S. Duez, S. Bernhardt, J. Heppekausen, F. F. Fleming, P. Knochel, Org. Lett., 2011,
13, 1690-1693.
α-Cyanohydrin triflates undergo Pd-catalyzed cross-coupling with aryl and vinyl
boronic acids under mild conditions. Coupling proceeds with complete inversion
of configuration at the stereogenic carbon. The resultant nitrile can be easily
converted into a variety of alternative functional groups of value in organic
synthesis and thus a high level of molecular diversity can be achieved.
A. He, J. R. Falck, J. Am. Chem. Soc., 2010,
132, 2524-2525.
α-Halonitriles react with alkyllithium, organomagnesium, and lithium dimethylcuprate reagents generating reactive, metalated nitriles. The rapid halogen-metal exchange with alkyllithium and Grignard reagents allows Barbier-type reactions with various electrophiles.
F. F. Fleming, Z. Zhang, W. Liu, P. Knochel, J. Org. Chem.,
2005,
70, 2200-2005.
A low loading of a proazaphosphatrane compound efficiently catalyzes the reaction of trimethylsilylacetonitrile
(TMSAN) with
aldehydes for the synthesis of
β-hydroxynitriles under mild reaction conditions. Various functional groups were tolerated, and good to excellent yields were obtained.
K. Wadhwa, J. G. Verkade, J. Org. Chem., 2009,
74, 5683-5686.
A general method for the direct α-arylation of nitriles with aryl chlorides
was developed. With a catalytic system generated from palladium and a commercially available
ligand, it is now possible to effect direct α-arylation using a wide variety of
starting materials.
J. You, J. G. Verkade, Angew. Chem., 2003,
115, 5205-5207.
Knoevenagel condensation followed by hydrogenation with triethylamine-formic
acid in the presence of a ruthenium-amido complex allowed an α-alkylation of
various nitriles with carbonyl compounds in good yields. The reaction tolerated
various functional groups, including nitro and chloro groups, and a furan ring.
H. Sun, D. Ye, H. Jiang, K. Chen, H. Liu, Synthesis, 2010,
2577-2582.
Benzylic, allylic, and aliphatic alcohols without β-branching have been converted to nitriles with two more carbon atoms than present in the substrate by treatment with an excess of (cyanomethyl)trimethylphosphonium iodide and subsequent in situ hydrolysis of the intermediate C-alkylated (cyanomethyl)phosphonium salts.
F. Zaragoza, J. Org. Chem, 2002, 67, 4963-4964.
