On the Unique Reactivity of Pd(OAc)₂ with Organic Azides: Expedient Synthesis of Nitriles and Imines

Abstract

As good as it gets: Pd(OAc)2 is a highly efficient catalyst for the transformation of primary azides into nitriles or imines under neutral, technical‐grade conditions, with unprecedented selectivities.

Efficient conversion of primary azides to aldehydes catalyzed by active site variants of myoglobin

“…1 Important and well established applications of azides in chemical synthesis include their use in Staudinger reductions, 2 Schmidt reactions 3 , Curtius rearrangements, 4 and metal-catalyzed dipolar cycloadditions with alkynes 5 to give triazoles. 1 More recently, azides have provided attractive substrates for the synthesis of nitriles 6 and C–H amination reactions via nitrene insertion. 7 A synthetically valuable but largely underexplored application of primary alkyl azides involves their oxidative transformation to aldehydes.…”

“…In particular, this transformation can provide a convenient, alternative route to the installation of aldehydes from a non-oxygenated precursor functional group. Unfortunately, the very few methods currently available to promote this transformation 9 require high catalyst loadings (e.g., 10 mol% MoO 2 (S 2 CNEt 2 ) 2 ) 9a,9b and harsh reaction conditions (reflux in toluene/water mixture) 9a , or they lack of selectivity for formation of the aldehyde product 6c …”

The trans–cis and the azide–tetrazole ring-chain isomerization of 2-azido-1,3-azoles: Quantum chemical study

“…[1]. Heterocyclic azides derivated from five-membered heteroarenes are known to spontaneously cyclization to form the isomeric bicyclic tetrazole.…”

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.…”