40231-42-3Relevant academic research and scientific papers
Iterative addition of carbon nucleophiles toN,N-dialkyl carboxamides for synthesis of α-tertiary amines
Chen, Jiahua,Chiba, Shunsuke,Lim, Jun Wei,Ong, Derek Yiren
, p. 99 - 104 (2022/01/06)
A protocol for the synthesis of α-tertiary amines was developed by iterative addition of carbon nucleophiles toN,N-dialkyl carboxamides. Nucleophilic 1,2-addition of organolithium reagents to carboxamides forms anionic tetrahedral carbinolamine (hemiaminal) intermediates, which are subsequently treated with bromotrimethylsilane (Me3SiBr) followed by organomagnesium (Grignard) reagents, organolithium reagents or tetrabutylammonium cyanide, affording α-tertiary amines. Employment of (trimethylsilyl)methylmagnesium bromide as the 2ndnucleophile allowed for aza-Peterson olefination of the resulting α-tertiary (trimethylsilyl)methylamines with acidic work-up, resulting in the formation of 1,1-diarylethylenes.
Electrochemical fluorosulfonylation of alkenes to access vicinal fluorinated sulfones derivatives
Zhao, Bin,Pan, Zichen,Zhu, Anqiao,Yue, Yanni,Ma, Mengtao,Xue, Fei
supporting information, (2022/01/24)
Herein, we report a practical and efficient fluorosulfonylation of the various alkenes with sulfonyl radical sources (RSO2NHNH2) and Et3N·3HF as cost-effective fluorination reagents under mild conditions. Remarkably, this
Photoredox-Catalyzed α-Aminomethyl Carboxylation of Styrenes with Sodium Glycinates: Synthesis of γ-Amino Acids and γ-Lactams
Zhou, Cong,Li, Miao,Sun, Jianwei,Cheng, Jiang,Sun, Song
supporting information, p. 2895 - 2899 (2021/05/05)
A visible-light photoredox-catalyzed reductive α-aminomethyl carboxylation of styrenes with sodium glycinates and CO2 has been developed to synthesize a series of α,α-disubstituted γ-amino acids and γ-lactams with high efficiency and regioselectivity. Notably, CO2 released from the decarboxylation step can be reused for the subsequent carboxylation. Distinct from the previous reactions with the same type of substrates leading to simple decarboxylation and olefin hydroalkylation, this process involves additional CO2 sequestration, thus leading to olefin α-aminomethyl carboxylation. These findings not only provide new access to α,α-disubstituted γ-amino acids and γ-lactams but also serve as a proof of concept for CO2 reutilization in decarboxylation reactions.
Direct Allylic C(sp3)?H and Vinylic C(sp2)?H Thiolation with Hydrogen Evolution by Quantum Dots and Visible Light
Huang, Cheng,Ci, Rui-Nan,Qiao, Jia,Wang, Xu-Zhe,Feng, Ke,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
supporting information, p. 11779 - 11783 (2021/04/21)
Direct allylic C?H thiolation is straightforward for allylic C(sp3)?S bond formation. However, strong interactions between thiol and transition metal catalysts lead to deactivation of the catalytic cycle or oxidation of sulfur atom under oxidative condition. Thus, direct allylic C(sp3)?H thiolation has proved difficult. Represented herein is an exceptional for direct, efficient, atom- and step-economic thiolation of allylic C(sp3)?H and thiol S?H under visible light irradiation. Radical trapping experiments and electron paramagnetic resonance (EPR) spectroscopy identified the allylic radical and thiyl radical generated on the surface of photocatalyst quantum dots (QDs). The C?S bond formation does not require external oxidants and radical initiators, and hydrogen (H2) is produced as byproduct. When vinylic C(sp2)?H was used instead of allylic C(sp3)?H bond, the radical-radical cross-coupling of C(sp2)?H and S?H was achieved with liberation of H2. Such a unique transformation opens up a door toward direct C?H and S?H coupling for valuable organosulfur chemistry.
Halogenation of 1,1-diarylethylenes by N-halosuccinimides
Zhang, Ge,Bai, Rui-Xue,Li, Chu-Han,Feng, Chen-Guo,Lin, Guo-Qiang
supporting information, p. 1658 - 1662 (2018/12/11)
An efficient method for the preparation of 2,2-diarylvinyl halides from the corresponding 1,1-diarylethylenes has been developed. N-Halosuccinimides (N-bromosuccinimide or N-chlorosuccinimide) were used as the halogenation reagents. The practicability of this method is highlighted by its simple operation, broad substrate scope and capability for large-scale reaction.
Photocatalytic, Phosphoranyl Radical-Mediated N-O Cleavage of Strained Cycloketone Oximes
Xia, Peng-Ju,Ye, Zhi-Peng,Hu, Yuan-Zhuo,Song, Dan,Xiang, Hao-Yue,Chen, Xiao-Qing,Yang, Hua
supporting information, p. 2658 - 2662 (2019/04/25)
A photoinduced, phosphoranyl radical-mediated protocol for the direct N-O cleavage of strained cycloketone oximes via a polar/SET crossover process was developed for the first time. This visible-light-driven direct N-O activation mode for oxime offers beneficial features such as streamlined synthetic process and versatile photochemical reactivities. Consequently, the alkenes and α-trifluoromethyl alkenes with varied electronic and structural features acted as competent radical receptors in this protocol, enabling facile accesses to a range of elongated cyano and/or gem-difluoroalkene-bearing compounds.
A convenient access to allylic triflones with allenes and triflyl chloride in the presence of (EtO)2P(O)H
Ni, Jixiang,Jiang, Yong,An, Zhenyu,Lan, Jingfeng,Yan, Rulong
supporting information, p. 7343 - 7345 (2019/06/27)
A simple method for the preparation of allylic triflones from allenes and triflyl chloride in the presence of (EtO)2P(O)H has been developed. The features of this reaction are catalyst-free and simple starting substrates. This method tolerates diverse functional groups and substituted allylic triflones are obtained in moderate to good yields.
Radical C?H Bond Trifluoromethylation of Alkenes by High-Valent Copper(III) Trifluoromethyl Compounds
Zhang, Hao-Ran,Xiao, Chang,Zhang, Song-Lin,Zhang, Xiaoming
supporting information, p. 5305 - 5310 (2019/11/22)
A general and selective method is developed that allows direct vinylic C?H bond trifluoromethylation of 1,1-diarylalkenes by a high-valent copper(III) trifluoromethyl complex, producing biologically active trifluoromethylated alkenes (as well as trifluoro
Traceless directing group mediated branched selective alkenylation of unbiased arenes
Agasti, Soumitra,Dey, Aniruddha,Maiti, Debabrata
supporting information, p. 12191 - 12194 (2016/10/21)
Owing to the synthetic importance of branched olefinated products, we report palladium catalyzed formation of branched olefins facilitated by a C-H activation based protocol. This involves selective insertion of olefins and subsequent decarboxylation using a completely unbiased benzene ring as the starting precursor. The significance of the protocol has been further highlighted by exhibition of functionality tolerance along with a late-stage modification of the branched olefinated products leading to the formation of other functionalized molecules.
Gold(I)-catalyzed decarboxylation of propargyl carbonates: Reactivity reversal of the gold catalyst from π-Lewis acidity to σ-Lewis acidity
Shen, Ruwei,Yang, Jianjun,Zhu, Shugao,Chen, Chao,Wu, Luling
, p. 1259 - 1269 (2015/04/22)
A cationic gold(I)-catalyzed decarboxylative etherification of propargyl carbonates to selectively produce propargyl ethers is reported. In the reaction the gold(I) catalyst shows a distinct σ-Lewis acidity rather than the commonly observed π-Lewis acidity, and thus catalyzes the decarboxylation of a variety of propargyl carbonates to give the corresponding propargyl ethers with high selectivity. This reaction represents a rare example of the tunable reactivity of cationic gold(I) complexes between σ-Lewis acidity and π-Lewis acidity.
