From Azides to Nitriles. A Novel Fast Transformation Made Possible by BrF₃

Abstract

[reaction: see text]. Various alkyl and aryl azides, readily obtained from halides or alcohols, were transformed into the corresponding nitriles using bromine trifluoride in moderate to good yields. The reaction is general and gives positive results with aliphatic, aromatic, cyclic, and functionalized azides. It can also be applied to the synthesis of optically active nitriles.

Toluene Dioxygenase‐Catalysed Oxidation of Benzyl Azide to Benzonitrile: Mechanistic Insights for an Unprecedented Enzymatic Transformation

“…[1] In recent years, the oxidative transformation of alkyl azides into nitriles has attracted much attention;i ti sa ni nteresting approach for the synthesis of nitrilesb ecause it does not require elongation of the skeletal carbon chain.S everalm ethods for this transformation have used stoichiometric oxidant, with or withoutacatalyst, for example, BrF 3 , [2] bis(acetoxy)iodobenzene, [3] 2,3-dichloro-5,6-dicyanobenzoquinone, [4] tert-butylhydroperoxide, [5] Pd(OAc) 2 , [6] Ru(OH)x/Al 2 O 3 [7] ande lectrochemical anodic oxidation. [1] In recent years, the oxidative transformation of alkyl azides into nitriles has attracted much attention;i ti sa ni nteresting approach for the synthesis of nitrilesb ecause it does not require elongation of the skeletal carbon chain.S everalm ethods for this transformation have used stoichiometric oxidant, with or withoutacatalyst, for example, BrF 3 , [2] bis(acetoxy)iodobenzene, [3] 2,3-dichloro-5,6-dicyanobenzoquinone, [4] tert-butylhydroperoxide, [5] Pd(OAc) 2 , [6] Ru(OH)x/Al 2 O 3 [7] ande lectrochemical anodic oxidation.…”

Rhodium Catalyzed ortho‐Cyanation of Arylphosphates with N‐cyano‐N‐phenyl‐p‐toluenesulfonamide

“…However, general problems in these reactions are the use of expensive aryl halides, highly toxic cyanating reagents, high catalyst loading due to the cyanide poisoning or need for superstoichiometric amounts of additives (generally metal salts), and harsh reaction conditions 7. Alternatively, aryl nitriles can be prepared by the dehydration approach, for example, dehydration of aryl amides or oximes,2a,b, 3a,b or oxidative dehydration of benzylic amines or alcohols with ammonia 9–10. Selective cyanation of highly abundant CH bonds with a suitable reagent is probably the most economic and benign route to the synthesis of aryl nitrile derivatives.…”

Inside Cover: Identification of Chiral Alkenyl‐ and Alkynylcarbinols as Pharmacophores for Potent Cytotoxicity (ChemMedChem 11/2013)

“…Azides allow the cyanide‐free preparation of nitriles with no elongation of the skeletal carbon chain under several conditions: strong stoichiometric oxidants (such as BF 3 ,5a 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ),5b,c or KI/ tert ‐butyl hydroperoxide),5d CuSO 4 /phenyliodonium diacetate,6 CuI/ tert ‐butyl hydroperoxide,7 or a supported RuOH catalyst 8. An earlier report, which employed palladium on charcoal with an alkyne as a hydrogen acceptor, caught our attention for its neutral conditions and its scope, which was not restricted to the formation of benzonitrile derivatives [Eq.…”