A non-metal catalysed oxidation of primary azides to nitriles at ambient temperature

Abstract

A novel non-metal catalyzed oxidation of organic azides to nitriles under solvent-free conditions is presented employing catalytic amounts of KI, and DABCO in aq. TBHP at room temperature. This non-metal catalyzed oxidation of azides provides good selectivity as double and triple bonds were not oxidized under the present reaction conditions.

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.…”

“…Research on new methodologies for the preparation of nitriles is of high interestt ot he organic chemistry community,b ecause they are considered very useful buildingb locks for the preparation of pharmaceuticals and functionalm aterial. [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. [8] Recently,w ereportedt he structures of novel interesting azido diols (Scheme 1) obtained from the biotransformation of benzyla zide by the toluened ioxygenase( TDO) enzymatic complex from Pseudomonas putida F1 expressed in Escherichia coli JM109 (pDTG601).…”

Flux-mediated syntheses, structural characterization and low-temperature polymorphism of the p-type semiconductor Cu2Ta4O11

“…Symmetry-lowering transitions driven by d 0 cations in an octahedral coordination are known to occur as a result of a second-order Jahn-Teller effects [46]. The driving force for a second-order Jahn-Teller distortion is expected to increase as the energy separation between the metal-based t 2g d-orbitals and the non-bonding O 2p states decrease [47].…”

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.…”