816-11-5Relevant articles and documents
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Cregge,R.J. et al.
, p. 2425 - 2428 (1973)
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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.
mCPBA-mediated dioxygenation of unactivated alkenes for the synthesis of 5-imino-2-tetrahydrofuranyl methanol derivatives
Deng, Xiaojun,Zhang, Luwen,Liu, Huixia,Bai, Yu,He, Wei
supporting information, (2020/11/24)
A mCPBA-mediated, metal-free, intramolecular dioxygenation reaction of unactivated alkenes is reported. In the presence of m-chlorobenzoic peracid, different unsaturated amide substrates could be cyclized via epoxide intermediates, producing the corresponding 5-imino-2-tetrahydrofuranyl methanol products in up to 94% yield at room temperature.