65854-92-4Relevant academic research and scientific papers
Nickel(II)- And Silver(I)-Catalyzed C-H Bond Halogenation of Anilides and Carbamates
Kianmehr, Ebrahim,Afaridoun, Hadi
, p. 1513 - 1523 (2020/12/14)
ortho -C-H bond halogenation of anilides and N -aryl carbamates using easily available N -halosuccinimides (NXS) as the active halogenation reagent in the presence of nickel or silver catalyst has been developed. This method provides a new approach to 2-haloanilides and carbamates, which may serve as starting materials for the synthesis of pharmaceutically and biologically active compounds.
Pd-Catalyzed Carbonylative Synthesis of 4H-Benzo[d][1,3]Oxazin-4-Ones Using Benzene-1,3,5-Triyl Triformate as the CO Source
Zheng, Yan,Dong, Mengke,Qu, Erdong,Bai, Jin,Wu, Xiao-Feng,Li, Wanfang
supporting information, p. 16219 - 16224 (2021/10/06)
A facile synthesis of 4H-benzo[d][1,3]oxazin-4-one derivatives by Pd-catalyzed carbonylative cross-coupling between N-(ortho-bromoaryl)amides and benzene-1,3,5-triyl triformate (TFBen) was developed. This procedure does not require the toxic and flammable gas CO as the carbonyl source and tolerates a wide scope of functional groups. Remarkably, 4H-benzo[d][1,3]oxazin-4-ones incorporated to natural products and drugs can be constructed by this method.
Equivalent Loading of Directed Arenes in Pd(II)-Catalyzed Oxidative Cross-Coupling of Aryl C-H Bonds at Room Temperature
Mei, Chong,Zhao, Mengdi,Lu, Wenjun
, p. 2714 - 2733 (2021/02/01)
The unsymmetrical biaryls (Ar1-Ar2) produced by the catalytic cross-couplings of aryl halides (Ar1-halo) with aryl metallics (Ar2-M) in the loading ratio of 1:1 are popular in chemical synthesis. In contrast, there has been less precedence on the same biaryls produced effectively from two normal aryl C-H bonds with equivalent loading. Here, we report that, in a palladium/oxidant/acid catalytic system at room temperature, one arene (Ar1-H, 1 equiv) can highly selectively couple with the other one (Ar2-H, 1 equiv) to afford the target Ar1-Ar2 just by controlling the directing groups and the substituted groups on their phenyl rings. The utility of this one-one cross-coupling is also demonstrated by synthesis of a few bioactive molecules.
Novel and efficient heterogeneous polymer supported copper catalyst for synthesis of 2-substituted Benzoxazoles from 2-Haloanilides
Saranya, Thachora Venu,Sruthi, Pambingal Rajan,Raj, Veena,Anas, Saithalavi
supporting information, (2021/02/27)
A novel polymer supported copper complex is prepared by the immobilization of copper iodide on chemically modified polyacrylonitrile and its application in heterogeneous catalysis is described. The catalyst was prepared by easy method via synthetic modification of Polyacrylonitrile (PAN) using ethylene diamine followed by the complexation with CuI. After characterization, this complex was explored as a green and efficient heterogeneous catalyst for the synthesis of 2-benzoxazoles from 2-haloanilides. The reaction was performed without adding additional ligand and the catalyst shows activity over a broad range of substrates with quantitative product yields. The catalyst was easily recovered by simple filtration and reused successfully for further cycle.
Photocatalyst- And Transition-Metal-Free Visible-Light-Promoted Intramolecular C(sp2)-S Formation
Wang, Hao,Wu, Qi,Zhang, Jian-Dong,Li, Hai-Yan,Li, Hong-Xi
supporting information, p. 2078 - 2083 (2021/04/05)
A photocatalyst- and transition-metal-free visible-light-induced cyclization of ortho-halothiobenzanilides has been developed. Upon irradiation with visible light, substrates undergo dehalogenative cyclization to 2-aryl benzothiazoles with high efficiency and selectivity. This photocyclization exhibits a high tolerance to various functional groups, is applicable for the synthesis of 2-alkyl benzothiazoles, and is easy to set up for gram-scale reaction.
Site-Selective C–H Functionalization of (Hetero)Arenes via Transient, Non-symmetric Iodanes
Fosu, Stacy C.,Hambira, Chido M.,Chen, Andrew D.,Fuchs, James R.,Nagib, David A.
supporting information, p. 417 - 428 (2019/02/14)
Fosu, Hambira, and colleagues describe the direct C–H functionalization of medicinally relevant arenes or heteroarenes. This strategy is enabled by transient generation of reactive, non-symmetric iodanes from anions and PhI(OAc)2. The site-selective incorporation of Cl, Br, OMs, OTs, and OTf to complex molecules, including within medicines and natural products, can be conducted by the operationally simple procedure included herein. A computational model for predicting site selectivity is also included. The discovery of new medicines is a time- and labor-intensive process that frequently requires over a decade to complete. A major bottleneck is the synthesis of drug candidates, wherein each complex molecule must be prepared individually via a multi-step synthesis, frequently requiring a week of effort per molecule for thousands of candidates. As an alternate strategy, direct, post-synthetic functionalization of a lead candidate could enable this diversification in a single operation. In this article, we describe a new method for direct manipulation of drug-like molecules by incorporation of motifs with either known pharmaceutical value (halides) or that permit subsequent conversion (pseudo-halides) to medicinally relevant analogs. This user-friendly strategy is enabled by combining commercial iodine reagents with salts and acids. We expect this simple method for selective, post-synthetic incorporation of molecular diversity will streamline the discovery of new medicines. A strategy for C–H functionalization of arenes and heteroarenes has been developed to allow site-selective incorporation of various anions, including Cl, Br, OMs, OTs, and OTf. This approach is enabled by in situ generation of reactive, non-symmetric iodanes by combining anions and bench-stable PhI(OAc)2. The utility of this mechanism is demonstrated via para-selective chlorination of medicinally relevant arenes, as well as site-selective C–H chlorination of heteroarenes. Spectroscopic, computational, and competition experiments describe the unique nature, reactivity, and selectivity of these transient, unsymmetrical iodanes.
ERBB/BTK INHIBITORS
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Page/Page column 198; 60, (2019/08/26)
Disclosed are compounds inhibiting ErbBs (e. g., EGFR or Her 2), especially mutant forms of ErbBs, and BTK, pharmaceutically acceptable salts, hydrates, solvates or stereoisomers thereof and pharmaceutical compositions comprising the compounds. The compou
Facile synthesis of 2-benzoxazoles via CuI/2,2'-bipyridine catalyzed intramolecular C–O coupling of 2-haloanilides
Venu Saranya, Thachora,Rajan Sruthi, Pambingal,Anas, Saithalavi
supporting information, p. 297 - 307 (2019/01/18)
Development of newer methods for the synthesis of Benzoxazoles has of greater interest due to their wide range of biological activities and pharmaceutical importance. We herein report a facile and general method for the synthesis of 2-substituted Benzoxazoles via copper catalyzed intramolecular C–O cross-coupling of 2-haloanilides. A combination of CuI (5 mol%), 2,2'-bipyridine (10 mol%), Cs2CO3 (2 equiv.) in DMF solvent with 4 ? molecular sieves at 140 °C, illustrated the scope for tuning the reactivity of 2-haloanilides toward the selective formation of a series of 2-alkyl benzoxazole derivatives in moderate to good yields. This is the first systematic study using CuI/2,2'-Bipyridine as the catalytic system for the synthesis of 2-substituted Benzoxazoles. The outcome of the reaction was found to be significantly influenced by the aromatic and amide substituents of 2-haloanilides.
Domino Pd0-Catalyzed C(sp3)–H Arylation/Electrocyclic Reactions via Benzazetidine Intermediates
Rocaboy, Ronan,Dailler, David,Zellweger, Florian,Neuburger, Markus,Salomé, Christophe,Clot, Eric,Baudoin, Olivier
, p. 12131 - 12135 (2018/09/11)
The Pd0-catalyzed C(sp3)-H arylation of 2-bromo-N-methylanilides leads to unstable benzazetidine intermediates that rearrange to benzoxazines through 4π electrocyclic ring-opening and 6π electrocyclization. The introduction of a bulky, non-activatable amide group on the nitrogen atom was key to favor the challenging reductive elimination step and disfavor undesired reaction pathways.
Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
Kathiravan, Subban,Nicholls, Ian A.
supporting information, p. 7031 - 7036 (2017/05/29)
Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
