69790-46-1Relevant articles and documents
Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones
Tang, Jing-Jing,Yu, Xiaoqiang,Wang, Yi,Yamamoto, Yoshinori,Bao, Ming
, p. 16426 - 16435 (2021/05/13)
Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C?H amidations strategies, an intermolecular regioselective C?H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.
Benzyl C–O and C–N Bond Construction via C–C Bond Dissociation of Oxime Ester under Visible Light Irradiation
Fan, Xiuwei,Lei, Tao,Liu, Zan,Yang, Xiu-Long,Cheng, Yuan-Yuan,Liang, Ge,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
, p. 1551 - 1558 (2019/09/09)
A photoredox benzyl activation was developed via formidable C(sp3)–C(sp3) bond dissociation of 1-aryl acetone oxime esters, which were easily prepared from benzyl ketones. Further coupling with O- and N- nucleophiles successfully forged important benzyl ether and amines derivatives in one pot. In this process, different substitutions on oxime esters were found compatible and various primary and secondary alcohols and amines, as well as amides showed good performance as nucleophiles. Mechanistic studies by control experiments, electrochemical measurements and in-situ NMR spectra proposed a N–O bond interruption/C–C bond fragmentation/oxidation sequence to provide the key cation intermediate for the next electrophilic SN process. The features of mild condition, short reaction time and broad substrate scope made this new strategy much promising in the transformation of benzyl compounds, which might be valuable in last-stage functionalizations.
Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
supporting information, p. 3940 - 3944 (2016/07/21)
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.