85092-84-8Relevant articles and documents
The Marriage of Carborane with Chalcogen Atoms: Nonconjugation, σ-πConjugation, and Intramolecular Charge Transfer
Yang, Xiaodong,Zhang, Bingjie,Zhang, Sikun,Li, Guoping,Xu, Letian,Wang, Zhijun,Li, Pengfei,Zhang, Yanfeng,Liu, Zishun,He, Gang
, p. 8285 - 8289 (2019)
A series of chalcogen-containing carborane derivatives were synthesized through a one-pot reaction. The nonconjugated six-membered ring of carborane-fused disulfide (1) can be electrochemically reduced to a dithiolate derivative. The five-membered ring of carborane-fused chalcogenophenes (2-4) showed aromaticity and considerable σ-πconjugation. The dicarborane chalcogenides (5-7) showed intramolecular charge-transfer-induced emission. These chalcogen-containing carborane derivatives provided a useful platform to study the electron interaction systematically and shed some light on the design of carborane-based optoelectronic materials.
Electrochemical Iodoamination of Indoles Using Unactivated Amines
Lei, Ning,Shen, Yanling,Li, Yujun,Tao, Pan,Yang, Liquan,Su, Zhishan,Zheng, Ke
, p. 9184 - 9189 (2020)
An environmentally friendly electrochemical approach for iodoamination of various indole derivatives with a series of unactivated amines, amino acid derivatives, and benzotriazoles (more than 80 examples) has been developed. This strategy was further applied in late-stage functionalization of natural products and pharmaceuticals and gram-scale synthesis and radiosynthesis of 131I-labeled compounds. Fundamental insights into the mechanism of the reaction based on control experiments, density functional theory calculation, and cyclic voltammetry are provided.
PIKFYVE KINASE INHIBITORS
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Page/Page column 386, (2021/08/20)
The present invention relates to compounds useful as inhibitors of phosphatidylinositol-3-phosphate 5-kinase (PIKfyve) as well as their use for treating diseases and disorders associated with PIKfyve.
Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
, p. 10422 - 10428 (2021/07/26)
The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
Short Synthesis of Oxetane and Azetidine 3-Aryl-3-carboxylic Acid Derivatives by Selective Furan Oxidative Cleavage
Bull, James A.,Choi, Chulho,Dubois, Maryne A. J.,Lee Wei Jie, Alvin,Mousseau, James J.,Smith, Milo A.,White, Andrew J. P.
supporting information, p. 5279 - 5283 (2020/08/14)
Four-membered rings remain underexplored motifs despite offering attractive physicochemical properties for medicinal chemistry. Arylacetic acids bearing oxetanes, azetidines, and cyclobutanes are prepared in two steps: a catalytic Friedel-Crafts reaction from four-membered ring alcohol substrates, followed by mild oxidative cleavage. The suitability of the products as building blocks is reflected in their facile purification and amenability to derivatization. Examples include heteroaromatics and aryltriflates, as well as oxetane-derived profen drug analogues and a new endomorphin derivative containing an azetidine amino acid residue.
Direct electrosynthesis for: N-alkyl-C3-halo-indoles using alkyl halide as both alkylating and halogenating building blocks
Sun, Linhao,Zhang, Xing,Wang, Chenguang,Teng, Huailong,Ma, Jimei,Li, Zilong,Chen, Hao,Jiang, Hong
supporting information, p. 2732 - 2738 (2019/06/13)
An electrochemically induced tandem reaction has been developed for selective N1-alkylation and C3-halogenation of indoles. This electrochemical difunctionalization strategy circumvents conventional multi-step procedures and efficiently generates syntheti
Mechanistic and experimental study on copper-catalyzed C3-sulfenylation of indoles with sulfur powder and aryl iodides
Ge, Xin,Cheng, Lin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
, p. 32 - 37 (2019/02/19)
The copper-catalyzed sulfenylation of indoles with aryl iodide and sulfur powder has been investigated both experimentally and theoretically. This protocol provides a direct and facile approach to prepare 3-sulfenylindoles with moderate to excellent yields and good functional-group tolerance. The in-situ IR analysis provided evidence for that NaOAc could promote the synthesis of diphenyl disulfide by the coupling of aryl iodide and sulfur powder. According to DFT calculations, the coupling pathway involving the intermediate N-methyl-3-iodoindole is more favored than the direct coupling by the C–H activation of indole. The N-methyl-3-iodoindole was identified as a crucial intermediate in the catalytic cycle.
Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols
Motsch, Sebastian,Schütz, Christian,Huy, Peter H.
supporting information, p. 4541 - 4547 (2018/09/13)
Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.
PhI(OAc)2/NaX-mediated halogenation providing access to valuable synthons 3-haloindole derivatives
Himabindu, Vittam,Parvathaneni, Sai Prathima,Rao, Vaidya Jayathirtha
, p. 18889 - 18893 (2018/11/27)
This paper describes a mild phenyliodine diacetate mediated method for selective chlorination, bromination, and iodination of indole C-H bonds using sodium halide as a source for analogous halogenations. The combination of NaX and phenyliodine diacetate provides an invincible system for halogenation of indoles. This protocol was compatible with a wide array of indole substrates and provides straight forward access to potential halogenated arenes.
Transition-Metal-Free Decarboxylative Iodination: New Routes for Decarboxylative Oxidative Cross-Couplings
Perry, Gregory J. P.,Quibell, Jacob M.,Panigrahi, Adyasha,Larrosa, Igor
supporting information, p. 11527 - 11536 (2017/08/30)
Constructing products of high synthetic value from inexpensive and abundant starting materials is of great importance. Aryl iodides are essential building blocks for the synthesis of functional molecules, and efficient methods for their synthesis from chemical feedstocks are highly sought after. Here we report a low-cost decarboxylative iodination that occurs simply from readily available benzoic acids and I2. The reaction is scalable and the scope and robustness of the reaction is thoroughly examined. Mechanistic studies suggest that this reaction does not proceed via a radical mechanism, which is in contrast to classical Hunsdiecker-type decarboxylative halogenations. In addition, DFT studies allow comparisons to be made between our procedure and current transition-metal-catalyzed decarboxylations. The utility of this procedure is demonstrated in its application to oxidative cross-couplings of aromatics via decarboxylative/C-H or double decarboxylative activations that use I2 as the terminal oxidant. This strategy allows the preparation of biaryls previously inaccessible via decarboxylative methods and holds other advantages over existing decarboxylative oxidative couplings, as stoichiometric transition metals are avoided.
