6639-27-6Relevant academic research and scientific papers
Photoswitchable azo‐ and diazocine‐functionalized derivatives of the vegfr‐2 inhibitor axitinib
Heintze, Linda,Schmidt, Dorian,Rodat, Theo,Witt, Lydia,Ewert, Julia,Kriegs, Malte,Herges, Rainer,Peifer, Christian
, p. 1 - 23 (2020/11/30)
In this study, we aimed at the application of the concept of photopharmacology to the approved vascular endothelial growth factor receptor (VEGFR)‐2 kinase inhibitor axitinib. In a previous study, we found out that the photoisomerization of axitinib’s stilbene‐like double bond is unidirectional in aqueous solution due to a competing irreversible [2+2]‐cycloaddition. Therefore, we next set out to azologize axitinib by means of incorporating azobenzenes as well as diazocine moieties as photoresponsive elements. Conceptually, diazocines (bridged azobenzenes) show favorable photoswitching properties compared to standard azobenzenes because the thermodynamically stable Z‐isomer usually is bioinactive, and back isomerization from the bioactive E‐isomer occurs thermally. Here, we report on the development of different sulfur– diazocines and carbon–diazocines attached to the axitinib pharmacophore that allow switching the VEGFR‐2 activity reversibly. For the best sulfur–diazocine, we could verify in a VEGFR‐2 kinase assay that the Z‐isomer is biologically inactive (IC50 >> 10,000 nM), while significant VEGFR‐2 inhibition can be observed after irradiation with blue light (405 nm), resulting in an IC50 value of 214 nM. In summary, we could successfully develop reversibly photoswitchable kinase inhibitors that exhibit more than 40‐fold differences in biological activities upon irradiation. Moreover, we demonstrate the potential advantage of diazocine photoswitches over standard azobenzenes.
TEMPO catalyzed oxidative dehydrogenation of hydrazobenzenes to azobenzenes
Fan, Baomin,Laishram, Ronibala Devi,Li, Jiayan,Luo, Yang,Lv, Haiping,More, Sagar,Su, Zhimin,Xu, Dandan,Yang, Yong,Zhan, Yong
supporting information, p. 3471 - 3474 (2020/05/25)
A metal-free direct oxidative dehydrogenation approach for the synthesis of azobenzenes from hydrazobenzenes has been developed by using TEMPO as an organocatalyst for the first time. The reaction proceeded in open air under mild reaction conditions. A wide range of hydrazobenzenes readily undergo dehydrogenation to give the corresponding azobenzenes in excellent yields.
Photocatalyzed oxidative dehydrogenation of hydrazobenzenes to azobenzenes
Lv, Haiping,Laishram, Ronibala Devi,Li, Jiayan,Zhou, Yongyun,Xu, Dandan,More, Sagar,Dai, Yuze,Fan, Baomin
supporting information, p. 4055 - 4061 (2019/08/07)
Visible light mediated oxidative dehydrogenation of hydrazobenzenes under an ambient atmosphere using an organic dye as a photocatalyst was reported for the first time. The reaction provides an environmentally benign method for the preparation of azobenzenes in excellent yields with good functional group tolerance.
Preparation method of aromatic azo organic compounds
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Paragraph 0027, (2019/12/25)
The invention discloses a preparation method of aromatic azo compounds so as to achieve high-yield preparation of the azo compounds from diaryl hydrazine low in cost and easy to obtain through oxydehydrogenation by an organic oxidant. According to different raw materials, the symmetrical or asymmetric azo compounds can be obtained, a catalyst is not needed, the reaction raw materials and the organic oxidant are low in cost and easy to obtain, conditions are mild and efficient, a reaction can be complete through only a few minutes, the reaction process is smooth and safe, products are easy to separate, and the preparation method accords with the development concept of green chemistry.
Modular Synthetic Route to Monofunctionalized Porphyrin Architectures
Heitmann, Gernot,Dommaschk, Marcel,L?w, Roland,Herges, Rainer
supporting information, p. 5228 - 5231 (2016/11/02)
The synthesis of a borylated Ni2+ porphyrin and its application as a versatile precursor for building up functional ortho-substituted tetraaryl porphyrin architectures is reported. This precursor porphyrin provides the basis for efficient modul
High-Yield Lithiation of Azobenzenes by Tin-Lithium Exchange
Strueben, Jan,Lipfert, Matthias,Springer, Jan-Ole,Gould, Colin A.,Gates, Paul J.,S?nnichsen, Frank D.,Staubitz, Anne
supporting information, p. 11165 - 11173 (2015/11/10)
The lithiation of halogenated azobenzenes by halogen-lithium exchange commonly leads to substantial degradation of the azo group to give hydrazine derivatives besides the desired aryl lithium species. Yields of quenching reactions with electrophiles are therefore low. This work shows that a transmetalation reaction of easily accessible stannylated azobenzenes with methyllithium leads to a near-quantitative lithiation of azobenzenes in para, meta, and ortho positions. To investigate the scope of the reaction, various lithiated azobenzenes were quenched with a variety of electrophiles. Furthermore, mechanistic 119Sn NMR spectroscopic studies on the formation of lithiated azobenzenes are presented. A tin ate complex of the azobenzene was detected and characterized at low temperature.
Copper-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane
Xu, Song,Chen, Huan-Huan,Dai, Jian-Jun,Xu, Hua-Jian
supporting information, p. 2306 - 2309 (2014/05/20)
An efficient Cu-promoted reductive coupling of aryl iodides with 1,1,1-trifluoro-2-iodoethane has been developed. This reaction could occur in good yields under milder conditions as compared with previous studies. The reaction tolerated nitro, formyl, ester, ether, carbonyl, sulfonyl, and even azo groups.
4,4'-bipyridine as a unidirectional switching unit for a molecular pushing motor
Kallweit, Christine,Haberhauer, Gebhard,Woitschetzki, Sascha
supporting information, p. 6358 - 6365 (2014/06/09)
A chirality switch in which the intrinsic chirality of a 4,4'-bipyridine is combined with a metal-ion-induced switching principle is described. In the uncomplexed state the 4,4'-bipyridine unit, which is linked to an S,S,S,S-configured cyclic imidazole peptide, is P-configured. The addition of zinc ions leads to a rotation around the C-C bond axis of the 4,4'-bipyridine and the Misomer of the metal complex is formed. By addition of a stronger complexing agent the metal ions are removed and the switch returns to its initial position. The combination of the chirality switch with a second switching unit allows the construction of a molecular pushing motor, which is driven chemically and by light. Motor drive: The combination of the intrinsic chirality of a 4,4'-bipyridine with a metal-ion-induced switching principle leads to a metal-ion-induced chirality switch that can also be used as a basic unit for a molecular pushing motor. Rotation around the C-C bond axis of the bipyridine, which is linked to a cyclic imidazole peptide, leads to switching between P and Misomers (see scheme).
A green procedure for the diazotization-iodination of aromatic amines under aqueous, strong-acid-free conditions
Trusova, Marina E.,Krasnokutskaya, Elena A.,Postnikov, Pavel S.,Choi, Younghwa,Chi, Ki-Whan,Filimonov, Victor D.
experimental part, p. 2154 - 2158 (2011/08/05)
A convenient and mild one-pot method for the synthesis of iodoarenes in high yields by the sequential diazotization-iodination of aromatic amines with a reusable polymeric diazotization agent in the presence of p-toluenesulfonic acid at room temperature in water was developed. The method is general and is the greenest alternative of the known diazotization-iodination methods. The method is also effective for the preparation of 1H-benzo[d][1,2,3]triazole and benzo[d][1,2,3]thiadiazole. Georg Thieme Verlag Stuttgart ? New York.
