40832-99-3Relevant articles and documents
Organic photoredox catalytic α-C(sp3)-H phosphorylation of saturated: Aza -heterocycles
Yi, Ming-Jun,Xiao, Teng-Fei,Li, Wen-Hui,Zhang, Yi-Fan,Yan, Pen-Ji,Zhang, Baoxin,Xu, Peng-Fei,Xu, Guo-Qiang
supporting information, p. 13158 - 13161 (2021/12/16)
A metal-free C(sp3)-H phosphorylation of saturated aza-heterocycles via the merger of organic photoredox and Br?nsted acid catalyses was established under mild conditions. This protocol provided straightforward and economic access to a variety of valuable α-phosphoryl cyclic amines by using commercially available diarylphosphine oxide reagents. In addition, the D-A fluorescent molecule DCQ was used for the first time as a photocatalyst and exhibited an excellent photoredox catalytic efficiency in this transformation. A series of mechanistic experiments and DFT calculations demonstrated that this transformation underwent a sequential visible light photoredox catalytic oxidation/nucleophilic addition process.
Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
supporting information, p. 3421 - 3426 (2020/06/25)
It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
Practical and regioselective amination of arenes using alkyl amines
Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
, p. 426 - 433 (2019/05/01)
The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.