Photochemical Mn-Mediated Generation of Azide Radicals for Improvement of Alkene Hydroxyazidation
Chen-Xi Xia1, Ziyang Li1, Ruyi Ye1
1Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, China.
Abstract:
State-of-the-art strategies for alkene-hydroxyazidation, which yield a mixture of β-azido alcohol and β-azido peroxide, must rely on phosphine reagents to improve the chemoselectivity. To overcome the above problems, we present a photochemical hydroxyazidation of alkenes via Mn-mediated ligand-to-metal charge transfer (LMCT) in O2, which activates N3- to •N3 and incorporates O2 to be used as an oxygen source in the hydroxyazidation products. Broad alkene range and step-economy chemistry for the hydroxyazidation transformation were also demonstrated.
Related Concept Videos
Oxidative Cleavage of Alkenes: Ozonolysis
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
Preparation of 1° Amines: Azide Synthesis
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Radical Anti-Markovnikov Addition to Alkenes: Overview
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide

![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
