An efficient transformation of primary halides into nitriles through palladium-catalyzed hydrogen transfer reaction.

Two-step one-pot transformation of primary halides into corresponding nitriles is successfully achieved. Nucleophilic substitution of primary halides with sodium azide and subsequent palladium-catalyzed hydrogen transfer proceeds smoothly in the presence of sterically bulky ligand dicyclohexyl(2',4',6'-triisopropylbiphenyl-2-yl)phosphine (XPhos) in acetone to produce nitriles in satisfactory to good yields.

[1]  R. Larock.  Comprehensive Organic Transformations , 1989 .

[2]  K. Ishihara,et al.  Rhenium(VII) oxo complexes as extremely active catalysts in the dehydration of primary amides and aldoximes to nitriles. , 2002, Angewandte Chemie.

[3]  Jason R. Schmink,et al.  Pd-catalyzed aldehyde to ester conversion: a hydrogen transfer approach. , 2013, Organic letters.

[4]  K. Rosenmund,et al.  Das am Ringkohlenstoff gebundene Halogen und sein Ersatz durch andere Substituenten. I. Mitteilung: Ersatz des Halogens durch die Carboxylgruppe , 1919 .

[5]  E. Scriven,et al.  Azides: their preparation and synthetic uses , 1988 .

[6]  K. R. Prabhu,et al.  An efficient oxidation of primary azides catalyzed by copper iodide: a convenient method for the synthesis of nitriles. , 2010, Angewandte Chemie.

[7]  M. Bao,et al.  Preparation and application of air-stable P,N-bidentate ligands for the selective synthesis of δ-lactone via the palladium-catalyzed telomerization of 1,3-butadiene with carbon dioxide , 2012 .

[8]  M. Beller,et al.  New catalytic properties of iron complexes: dehydration of amides to nitriles. , 2009, Chemical communications.

[9]  J. M. Williams,et al.  Palladium-catalyzed cyanation of aryl bromides promoted by low-level organotin compounds. , 2004, Organic letters.

[10]  Y. Liu,et al.  An investigation into causes and effects of high cyanide levels in the palladium-catalyzed cyanation reaction. , 2004, Organic letters.

[11]  N. Jiao,et al.  Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage. , 2014, Accounts of chemical research.

[12]  M. Taillefer,et al.  Mild and efficient copper-catalyzed cyanation of aryl iodides and bromides. , 2005, Chemistry.

[13]  C. Galli.  Radical reactions of arenediazonium ions: An easy entry into the chemistry of the aryl radical , 1988 .

[14]  R. Chidambaram.  A robust palladium-catalyzed cyanation procedure: beneficial effect of zinc acetate , 2004 .

[15]  J. Wang,et al.  Palladium-catalyzed direct cyanation of indoles with K(4)[Fe(CN)(6)]. , 2010, Organic letters.

[16]  L. Zhang,et al.  An efficient transformation from benzyl or allyl halides to aryl and alkenyl nitriles. , 2010, Organic letters.

[17]  L. Zhang,et al.  Direct transformation of methyl arenes to aryl nitriles at room temperature. , 2009, Angewandte Chemie.

[18]  M. Martinelli,et al.  A practical synthesis of 2-((1H-pyrrolo[2,3-b]pyridine-4-yl)methylamino)-5- fluoronicotinic acid. , 2006, Journal of Organic Chemistry.

[19]  K. Yamaguchi,et al.  Catalysis of a hydroxyapatite-bound Ru complex:efficient heterogeneous oxidation of primary amines to nitriles in thepresence of molecular oxygen , 2001 .

[20]  Zhentao Wang,et al.  A metal-free catalytic system for the oxidation of benzylic methylenes and primary amines under solvent-free conditions , 2009 .

[21]  Kak‐Shan Shia,et al.  A convenient new procedure for converting primary amides into nitriles. , 2007, Chemical communications.

[22]  R. Cherney,et al.  Mild and general methods for the palladium-catalyzed cyanation of aryl and heteroaryl chlorides. , 2007, Organic letters.

[23]  A. Fatiadi.  Preparation and synthetic applications of cyano compounds , 2010 .

[24]  D. Roe,et al.  Mechanisms of catalyst poisoning in palladium-catalyzed cyanation of haloarenes. remarkably facile C-N bond activation in the [(Ph3P)4Pd]/[Bu4N]+ CN- system. , 2008, Journal of the American Chemical Society.

[25]  Jianbin Chen,et al.  The palladium-catalyzed cyanation of indole C-H bonds with the combination of NH4HCO3 and DMSO as a safe cyanide source. , 2011, Chemical communications.

[26]  S. May,et al.  Development of Pd/C-catalyzed cyanation of aryl halides. , 2011, The Journal of organic chemistry.

[27]  J. Suh,et al.  Acaricidal activities of apiol and its derivatives from Petroselinum sativum seeds against Dermatophagoides pteronyssinus, Dermatophagoides farinae, and Tyrophagus putrescentiae. , 2011, Journal of agricultural and food chemistry.

[28]  O. Daugulis,et al.  Copper-catalyzed cyanation of heterocycle carbon-hydrogen bonds. , 2010, Organic letters.

[29]  R. Ohmura,et al.  Direct oxidative conversion of alkyl halides into nitriles with molecular iodine and 1,3-diiodo-5,5-dimethylhydantoin in aq ammonia , 2009 .

[30]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[31]  Xiaoqiang Yu,et al.  Efficient palladium-catalyzed cyanation of aryl/heteroaryl bromides with K4[Fe(CN)6] in t-BuOH–H2O using tris(2-morpholinophenyl)phosphine as a ligand , 2013 .

[32]  M. Beller,et al.  A new palladium catalyst system for the cyanation of aryl chlorides , 2001 .

[33]  M. Dai,et al.  Synthesis of nitriles via palladium-catalyzed water shuffling from amides to acetonitrile. , 2014, Organic & biomolecular chemistry.

[34]  N. Mizuno,et al.  A tungsten-tin mixed hydroxide as an efficient heterogeneous catalyst for dehydration of aldoximes to nitriles. , 2007, Angewandte Chemie.

[35]  R. Srivastava,et al.  Application of polymer-supported triphenyl phosphine in the palladium-catalyzed cyanation reaction under microwave conditions , 2004 .

[36]  C. Bertozzi,et al.  Cell surface engineering by a modified Staudinger reaction. , 2000, Science.

[37]  M. Beller,et al.  A general and convenient catalytic synthesis of nitriles from amides and silanes. , 2009, Organic letters.

[38]  K. R. Prabhu,et al.  A non-metal catalysed oxidation of primary azides to nitriles at ambient temperature. , 2012, Organic & biomolecular chemistry.

[39]  N. Jiao,et al.  Direct transformation of N,N-dimethylformamide to -CN: Pd-catalyzed cyanation of heteroarenes via C-H functionalization. , 2011, Journal of the American Chemical Society.

[40]  P. Jadhav,et al.  5-Amidinobenzo[b]thiophenes as dual inhibitors of factors IXa and Xa. , 2005, Bioorganic & medicinal chemistry letters.

[41]  W. Bailey,et al.  Facile oxidation of primary amines to nitriles using an oxoammonium salt. , 2014, Organic letters.

[42]  K. Gomi,et al.  Synthesis and antitumor activity of duocarmycin derivatives: A-ring pyrrole analogues of duocarmycin B2. , 1996, Bioorganic & medicinal chemistry.

[43]  W. Marshall,et al.  Why excess cyanide can be detrimental to Pd-catalyzed cyanation of haloarenes. Facile formation and characterization of [Pd(CN)(3)(H)](2-) and [Pd(CN)(3)(Ph)](2-). , 2007, Journal of the American Chemical Society.

[44]  C. So,et al.  A mild and efficient palladium-catalyzed cyanation of aryl mesylates in water or tBuOH/water. , 2010, Angewandte Chemie.

[45]  M. Häggblom,et al.  Biotransformation of 3,5‐dibromo‐4‐hydroxybenzonitrile under denitrifying, Fe(III)‐reducing, sulfidogenic, and methanogenic conditions , 2003, Environmental Toxicology and Chemistry.

[46]  Jiang Cheng,et al.  Chelation-assisted palladium-catalyzed direct cyanation of 2-arylpyridine C-H bonds. , 2009, Organic letters.

[47]  Kou-Chang Liu,et al.  3'-Arylspiro[isobenzofuran-1(3H),5'(4'H)-isoxazol]-3-ones and their conversion to 2-(3-arylisoxazol-5-yl)benzoates , 1983 .

[48]  M. Beller,et al.  Progress in the palladium-catalyzed cyanation of aryl chlorides. , 2003, Chemistry.

[49]  N. Mizuno,et al.  Aerobic oxidative transformation of primary azides to nitriles by ruthenium hydroxide catalyst. , 2011, The Journal of organic chemistry.

[50]  Sukbok Chang,et al.  A new combined source of "CN" from N,N-dimethylformamide and ammonia in the palladium-catalyzed cyanation of aryl C-H bonds. , 2010, Journal of the American Chemical Society.

[51]  B. Liu,et al.  The palladium-catalyzed desulfitative cyanation of arenesulfonyl chlorides and sodium sulfinates. , 2012, Chemical communications.

[52]  jin-quan yu,et al.  Cu(II)-catalyzed functionalizations of aryl C-H bonds using O2 as an oxidant. , 2006, Journal of the American Chemical Society.

[53]  M. Beller,et al.  Recent developments and perspectives in palladium-catalyzed cyanation of aryl halides: synthesis of benzonitriles. , 2011, Chemical Society reviews.

[54]  H. H. Hodgson.  The Sandmeyer reaction. , 1947, Chemical reviews.

[55]  G. Olah,et al.  Gallium (III) triflate catalyzed dehydration of aldoximes , 2005 .

[56]  M. Beller,et al.  A convenient and efficient procedure for the palladium-catalyzed cyanation of aryl halides using trimethylsilylcyanide , 2003 .

[57]  Giao T. M. Nguyen,et al.  Flexible Solid Polymer Electrolytes Based on Nitrile Butadiene Rubber/Poly(ethylene oxide) Interpenetrating Polymer Networks Containing Either LiTFSI or EMITFSI , 2011 .

[58]  Shota Tanaka,et al.  Ethylaluminum as an ethylene source for the Mizoroki-Heck-type reaction. Rhodium-catalyzed preparation of stilbene derivatives. , 2015, Chemical communications.

[59]  V. Grushin,et al.  Rational catalysis design on the basis of mechanistic understanding: highly efficient Pd-catalyzed cyanation of aryl bromides with NaCN in recyclable solvents. , 2011, Journal of the American Chemical Society.

[60]  N. Mizuno,et al.  Efficient heterogeneous aerobic oxidation of amines by a supported ruthenium catalyst. , 2003, Angewandte Chemie.

[61]  Chongmok Lee,et al.  [RuCl(2)(p-cymene)](2) on carbon: an efficient, selective, reusable, and environmentally versatile heterogeneous catalyst. , 2002, Organic letters.

[62]  J. Manson,et al.  Designer magnets containing cyanides and nitriles. , 2001, Accounts of chemical research.

[63]  N. Jiao,et al.  Iron-facilitated direct oxidative C-H transformation of allylarenes or alkenes to alkenyl nitriles. , 2010, Journal of the American Chemical Society.

[64]  N. Jiao,et al.  Direct transformation of methyl imines to α-iminonitriles under mild and transition-metal-free conditions. , 2013, Chemistry.

[65]  S. Díez‐González,et al.  On the Unique Reactivity of Pd(OAc)2 with Organic Azides: Expedient Synthesis of Nitriles and Imines , 2013, ChemCatChem.

[66]  J. Lindley.  Tetrahedron report number 163 , 1984 .

[67]  M. Beller,et al.  A convenient procedure for the palladium-catalyzed cyanation of aryl halides. , 2003, Angewandte Chemie.

[68]  L. E. Brown,et al.  Biomimetic syntheses of pretetramides. 2. A synthetic route based on a preformed D ring. , 1988, Journal of the American Chemical Society.