3469-00-9Relevant articles and documents
Engbersen,Engberts
, p. 1215 (1974)
Iodoarene-Catalyzed Oxyamination of Unactivated Alkenes to Synthesize 5-Imino-2-Tetrahydrofuranyl Methanamine Derivatives
Deng, Xiao-Jun,Liu, Hui-Xia,Zhang, Lu-Wen,Zhang, Guan-Yu,Yu, Zhi-Xiang,He, Wei
, p. 235 - 253 (2021/01/09)
Reported here is the room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes. In this process, the alkenes are difunctionalized by the oxygen atom of the amide group and the nitrogen in an exogenous HNTs2 molecule. This mild and open-air reaction provided an efficient synthesis to N-bistosyl-substituted 5-imino-2-tetrahydrofuranyl methanamine derivatives, which are important motifs in drug development and biological studies. Mechanistic study based on experiments and density functional theory calculations showed that this transformation proceeds via activation of the substrate alkene by an in situ generated cationic iodonium(III) intermediate, which is subsequently attacked by an oxygen atom (instead of nitrogen) of amides to form a five-membered ring intermediate. Finally, this intermediate undergoes an SN2 reaction by NTs2 as the nucleophile to give the oxygen and nitrogen difunctionalized 5-imino-2-tetrahydrofuranyl methanamine product. An asymmetric variant of the present alkene oxyamination using chiral iodoarenes as catalysts also gave promising results for some of the substrates.
Photoredox Catalytic Phosphite-Mediated Deoxygenation of α-Diketones Enables Wolff Rearrangement and Staudinger Synthesis of β-Lactams
Jiang, Zhiyong,Li, Haijun,Wei, Guo,Yang, Hui
supporting information, p. 19696 - 19700 (2021/08/03)
A novel visible-light-driven catalytic activation of C=O bonds by exploiting the photoredox chemistry of 1,3,2-dioxaphospholes, readily accessible from α-diketones and trialkyl phosphites, is reported. This mild and environmentally friendly strategy provides an unprecedented and efficient access to the Wolff rearrangement reaction which traditionally entails α-diazoketones as precursors. The resulting ketenes could be precisely trapped by alcohols/thiols to give α-aryl (thio)acetates and by imines to afford the valuable β-lactams in up to 99 % yields.