Palladium‐Catalyzed Intermolecular Oxidative Diazidation of Alkenes

Abstract

A palladium-catalyzed oxidative vicinal diazidation of alkenes has been developed, in which TMSN 3 was used as azide source. Both styrenes and unactivated alkenes are suitable for this reaction. And trans-alkyldiazides were obtained as major products from cyclic alkenes with moderate to good diastereoselectivities. This reaction afforded an efficient way for the synthesis of useful 1,2-diamines after hydrogenation.

Chemical versatility of azide radical: journey from a transient species to synthetic accessibility in organic transformations

“…In the same year, a new palladium-catalyzed oxidative transdiazidation method for styrenes and unactivated alkenes was described by Liu et al using the Pd(OTFA) 2 catalyst with the phenanthroline based ligand, NFSI oxidant, and TMSN 3 as the azide source (Scheme 10a). 96 Notably, moderate to good Later on, in 2019, Chu and co-workers reported the chemoselective and oxidative diazidation of alkenes enabled by the Fe(II)-catalyst with the appropriate choice of binary solvents (t-BuOH/DCM) (Scheme 10b). 97 Importantly, the addition of a polar protic co-solvent such as t-BuOH diminished the polarunmatched HAT with DCM solvent and produced azide radical in a more facile and controlled way from TMSN 3 , using di-tertbutyl peroxide (DTBP) as an oxidizing agent and Fe(II) catalyst.…”

Transition Metal Catalyzed Azidation Reactions

“…In 2017, Liu and co-workers developed a Pd(II)-catalyzed diazidation of olefins in oxidative conditions [107]. The optimal results were obtained working with Pd(TFA) 2 as a catalyst, TMS-N 3 as azide source, and NFSI as oxidant in the presence of the bidentate nitrogen ligand 4,7-di(4-bromophenyl)-1,10-phenanthroline 49.…”

Reactivity of Styrenes in Micelles: Safe, Selective, and Sustainable Functionalization with Azides and Carboxylic Acids

“…The α-functionalized ketone motifs, especially azidoketones and acyloxyketones, are valuable intermediates due to their broad synthetic utility to the pharmaceuticals, agrochemicals, and fine chemicals industries. − Therefore, various methods have been developed for their synthesis. The traditional approaches focus on either the substitution reaction of prefunctionalized starting materials or the oxidative coupling of carbonyl compounds in the presence of strong oxidants. − Among the most important synthetic methodologies for preparing azidoketones from alkenes involves TMSN 3 -CrO 3 and CAN/NaN 3 . , Likewise, oxidative coupling of alkenes and carboxylic acids to acyloxyketones has been reported using the I 2 / TBHP catalytic system . Recently, Reiser and co-workers have reported visible-light-accelerated oxyazidation of styrene derivatives using [Cu­(dap) 2 Cl] as the catalyst .…”