title: Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.
abstract: An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.
authors.forename: Xiang
authors.initials: X
authors.lastname: Sun
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.
authors.forename: Xinyao
authors.initials: X
authors.lastname: Li
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.
authors.forename: Song
authors.initials: S
authors.lastname: Song
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.
authors.forename: Yuchao
authors.initials: Y
authors.lastname: Zhu
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.
authors.forename: Yu-Feng
authors.initials: YF
authors.lastname: Liang
authors.affiliation: †State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Xue Yuan Rd. 38, Beijing 100191, China.|‡State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
authors.forename: Ning
authors.initials: N
authors.lastname: Jiao
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D001386:Azides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction
chemical_list: D000438:Alcohols; D000475:Alkenes; D001386:Azides; D009942:Organometallic Compounds; D008345:Manganese