1123-99-5Relevant academic research and scientific papers
Direct iodination of electron-deficient benzothiazoles: Rapid access to two-photon absorbing fluorophores with quadrupolar D-π-A-π-D architecture and tunable heteroaromatic core
Fakis, Mihalis,Georgiou, Dimitris,Hrobárik, Peter,Nociarová, Jela,Osusky, Patrik,Polyzos, Ioannis,Rakovsky, Erik
, p. 3460 - 3465 (2021)
Direct iodination of benzothiazoles under strong oxidative/acidic conditions leads to a mixture of iodinated heteroarenes with 1-2 major components, which are easily separable and which structures depend on the I2 equivalents used. Among the unexpected bu
Synthesis of C,N′-linked bis-heterocycles using a deprotometalation-iodination-N-arylation sequence and evaluation of their antiproliferative activity in melanoma cells
Hedidi, Madani,Bentabed-Ababsa, Ghenia,Derdour, A?cha,Roisnel, Thierry,Dorcet, Vincent,Chevallier, Floris,Picot, Laurent,Thiéry, Valérie,Mongin, Florence
, p. 3498 - 3507 (2014)
Benzothiophene, benzofuran, benzothiazole and benzoxazole were deprotometalated using the lithium-zinc combination prepared from ZnCl 2·TMEDA (TMEDA = N,N,N′,N′- tetramethylethylenediamine, 1 equiv) and lithium 2,2,6,6-tetramethylpiperidide (LiTMP, 3 equiv). Subsequent interception of the 2-metalated derivatives using iodine as electrophile led to the iodides in 81%, 82%, 67% and 42% yields, respectively. These yields are higher (10% more) than those obtained using ZnCl2·TMEDA (0.5 equiv) and LiTMP (1.5 equiv), except in the case of benzoxazole (10% less). The crude iodides were involved in the N-arylation of pyrrole, indole, carbazole, pyrazole, indazole, imidazole and benzimidazole in the presence of Cu (0.2 equiv) and Cs2CO3 (2 equiv), and using acetonitrile as solvent (no other ligand) to provide after 24 h reflux the expected N-arylated azoles in yields ranging from 33% to 81%. Using benzotriazole also led to N-arylation products, but in lower 34%, 39%, 36% and 6% yields, respectively. A further study with this azole evidenced the impact of 2,2,6,6-tetramethylpiperidine on the N-arylation yields. Most of the C,N′-linked bis-heterocycles thus synthesized (in particular those containing benzimidazole) induced a high growth inhibition of A2058 melanoma cells after a 72 h treatment at 10-5 M.
Combretastatin A-4 sulfur-containing heterocyclic derivatives: Synthesis, antiproliferative activities and molecular docking studies
Faouzi, Abdelfattah,Arnaud, Alexandre,Bancet, Alexandre,Barette, Caroline,Preto, Jordane,Do, Cong Viet,Jordheim, Lars Petter,Bousfiha, Zineb,Nguyen, Thi Thanh Binh,Verrière, Marion,Farce, Amaury,Fauvarque, Marie-Odile,Barret, Roland,Lomberget, Thierry
, (2021)
Combretastatin A-4 inspired heterocyclic derivatives were synthesized and evaluated for their biological activities on tubulin polymerization and cell proliferation. Among the 19 described sulfur-containing compounds, derivatives (Z)-4h and (Z)-4j exhibited interesting in cellulo tubulin polymerization inhibition and antiproliferative activities with IC50 values for six different cell lines between 8 and 27 nM. Furthermore, in silico docking studies within the colchicine/CA-4 binding site of tubulin were carried out to understand the interactions of our products with the protein target. The effects on the cell cycle of follicular lymphoma cells were also investigated at 1–10 nM concentrations showing that apoptotic processes occurred.
Walking Down the Chalcogenic Group of the Periodic Table: From Singlet to Triplet Organic Emitters
Kremer, Adrian,Aurisicchio, Claudia,Deleo, Federica,Ventura, Barbara,Wouters, Johan,Armaroli, Nicola,Barbieri, Andrea,Bonifazi, Davide
, p. 15377 - 15387 (2015)
The synthesis, X-ray crystal structures, ground- and excited-state UV/Vis absorption spectra, and luminescence properties of chalcogen-doped organic emitters equipped on both extremities with benzoxa-, benzothia-, benzoselena- and benzotellurazole (1
Ionic Reactivity of 2-Isocyanoaryl Thioethers: Access to 2-Halo and 2-Aminobenzothia/Selenazoles
Dong, Jinhuan,Hu, Junlin,Liu, Xiaoli,Sun, Shaoguang,Bao, Lan,Jia, Mengying,Xu, Xianxiu
, p. 2845 - 2852 (2022/02/23)
An ionic cascade insertion/cyclization reaction of thia-/selena-functionalized arylisocyanides has been successfully developed for the efficient and practical synthesis of 2-halobenzothiazole/benzoselenazole derivatives. This synthetic protocol, incorporating a halogen atom when forming the five-membered ring of benzothia/selenazoles, is different from the existing ones, where halogenation of the preformed benzothia/selenazole precursors happens. Additionally, a facile access to 2-aminobenzothiazoles is also achieved by the one-pot cascade reaction of 2-isocyanoaryl thioethers, iodine, and amines.
Preparation of Polyfunctional Arylzinc Organometallics in Toluene by Halogen/Zinc Exchange Reactions
Balkenhohl, Moritz,Ziegler, Dorothée S.,Desaintjean, Alexandre,Bole, Leonie J.,Kennedy, Alan R.,Hevia, Eva,Knochel, Paul
supporting information, p. 12898 - 12902 (2019/07/31)
A wide range of polyfunctional diaryl- and diheteroarylzinc species were prepared in toluene within 10 min to 5 h through an I/Zn or Br/Zn exchange reaction using bimetallic reagents of the general formula R′2Zn?2 LiOR (R′=sBu, tBu, pTol). Highly sensitive functional groups, such as a triazine, a ketone, an aldehyde, or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of a plethora of functionalized (hetero)arenes after quenching with various electrophiles. Insight into the constitution and reactivity of these bimetallic mixtures revealed the formation of highly active lithium diorganodialkoxyzincates of type [R′2Zn(OR)2Li2].
T -BuONa-mediated direct C-H halogenation of electron-deficient (hetero)arenes
Liu, Xia,Zhao, Xin,Liang, Fushun,Ren, Baoyi
supporting information, p. 886 - 890 (2018/02/19)
An efficient halogenation of electron-deficient (hetero)arenes is described. The reaction utilizes common t-BuONa as a catalyst (for iodination) or a promoter (for bromination and chlorination), and perfluorobutyl iodide, CBr4 or CCl4 as the readily-available halogenating agents, respectively. The protocol features broad scope, high efficiency, mild conditions and gram scalability. An ionic pathway involving halogen bond formation and halophilic attack is proposed. The utility of the resulting iodinated heteroarenes is demonstrated in visible light-mediated Caryl-Caryl cross-coupling reaction.
Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide
Mukhopadhyay, Sushobhan,Batra, Sanjay
supporting information, p. 14622 - 14626 (2018/09/21)
A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.
Method for preparing halogenated (hetero) aromatic hydrocarbons
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Paragraph 0033; 0034, (2018/03/24)
The invention relates to a method for preparing halogenated (hetero) aromatic hydrocarbons. The halogenated (hetero) aromatic hydrocarbons are prepared from cheap and easily available perfluorobutyl iodide, carbon tetrabromide and carbon tetrachloride as iodinated, brominated and chlorinated reagents respectively under the action of alkali catalysis (promotion). The method comprises the following steps: firstly, (hetero) aromatic hydrocarbons, a halogenated reagent and an inorganic base are placed in an organic solvent, stirred at room temperature and monitored with TLC until a substrate disappears, and the reaction is stopped; then, a reaction mixed solution is poured into water and extracted, an organic phase is dried, and the organic solvent is removed under reduced pressure; finally, silica-gel column chromatography is performed on a crude product, and a product is obtained. Purification can also be performed by recrystallization. The method has the advantages that the synthetic route is wide in substrate range, raw materials and reagents are cheap and easily available, operation is simple, conditions are mild, yield is high, energy consumption is reduced, the reaction route is safe, gram-grade preparation can be performed and the like.
Mechanistic Insights into Pincer-Ligated Palladium-Catalyzed Arylation of Azoles with Aryl Iodides: Evidence of a PdII-PdIV-PdII Pathway
Khake, Shrikant M.,Jagtap, Rahul A.,Dangat, Yuvraj B.,Gonnade, Rajesh G.,Vanka, Kumar,Punji, Benudhar
, p. 875 - 886 (2016/04/19)
Pincer-based (R2POCNR′2)PdCl complexes along with CuI cocatalyst catalyze the arylation of azoles with aryl iodides to give the 2-arylated azole products. Herein, we report an extensive mechanistic investigation for the direct arylation of azoles involving a well-defined and highly efficient (iPr2POCNEt2)PdCl (2a) catalyst, which emphasizes a rare PdII-PdIV-PdII redox catalytic pathway. Kinetic studies and deuterium labeling experiments indicate that the C-H bond cleavage on azoles occurs via two distinct routes in a reversible manner. Controlled reactivity of the catalyst 2a underlines the iodo derivative (iPr2POCNEt2)PdI (3a) to be the resting state of the catalyst. The intermediate species (iPr2POCNEt2)Pd-benzothiazolyl (4a) has been isolated and structurally characterized. A determination of reaction rates of compound 4a with electronically different aryl iodides has revealed the kinetic significance of the oxidative addition of the C(sp2)-X electrophile, aryl iodide, to complex 4a. Furthermore, the reactivity behavior of 4a suggests that the arylation of benzothiazole proceeds via an oxidative addition/reductive elimination pathway involving a (iPr2POCNEt2)PdIV(benzothiazolyl)(Ar)I species, which is strongly supported by DFT calculations.
