Elemental Sulfur-Mediated Decarboxylative Redox Cyclization ­Reaction: Copper-Catalyzed Synthesis of 2-Substituted Benzo­thiazoles

Synlett ◽  
2017 ◽  
Vol 29 (02) ◽  
pp. 219-224 ◽  
Author(s):  
Xin Wang ◽  
Xiaotong Li ◽  
Renhe Hu ◽  
Zhao Yang ◽  
Ren Gu ◽  
...  

A S8-mediated directed decarboxylative redox-cyclization strategy for the synthesis of 2-substituted benzothiazoles from o-iodoanilines, arylacetic acids, and elemental sulfur catalyzed by cheap copper metal has been developed. This reaction is operationally simple, ligand-free, compatible with a wide range of functional groups, and provides the desired products in good to excellent yields. In addition, a gram-scale experiment was carried out to furnish PMX 610, an antitumor drug.

2015 ◽  
Vol 17 (4) ◽  
pp. 976-978 ◽  
Author(s):  
Tirumaleswararao Guntreddi ◽  
Rajeshwer Vanjari ◽  
Krishna Nand Singh

Synthesis ◽  
2020 ◽  
Vol 52 (09) ◽  
pp. 1425-1434 ◽  
Author(s):  
Anil K. Saikia ◽  
Ngangbam Renubala Devi ◽  
Sudip Shit ◽  
Bipin Kumar Behera

An intramolecular Friedel–Crafts cyclization reaction catalyzed by indium(III) chloride for the formation of 4-vinyl-1,2,3,4-tetrahydroisoquinoline from N-tethered benzyl-alkenol in good yields has been described. The reaction is highly regioselective and generates an exocyclic vinyl functionality in the piperidine ring. The reaction is compatible with a wide range of functional groups. The strategy is demonstrated for the formal synthesis of (±)-isocyclocelabenzine alkaloid.


ChemInform ◽  
2015 ◽  
Vol 46 (28) ◽  
pp. no-no
Author(s):  
Tirumaleswararao Guntreddi ◽  
Rajeshwer Vanjari ◽  
Krishna Nand Singh

Synthesis ◽  
2021 ◽  
Author(s):  
Alexandre Desaintjean ◽  
Fanny Danton ◽  
Paul Knochel

A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents were prepared in toluene within 10 to 120 min between −78 °C and 25 °C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as a triazene or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arenes and alkenes derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.


Synthesis ◽  
2020 ◽  
Author(s):  
Feng Li ◽  
Hai Ma ◽  
Qing-he Zhao ◽  
Guang-hao Yu ◽  
Ye-chen Meng ◽  
...  

AbstractA series of (trifluoromethyl)cyclopropanes (TFCPs) tolerating a broad range of functional groups, known as tert-butyl bioisosteres, have been obtained from the cyclization reaction between nitromethane­ and 5-[β-(trifluoromethyl)styryl]isoxazoles in 70–94% yields and 75:25 to 90:10 dr. This method offers practical access to this cyclopropyl moiety of pharmacological interest, employing an inorganic base under phase-transfer conditions.


Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2425-2428 ◽  
Author(s):  
Bill Morandi ◽  
Yong Lee

We report that a Lewis acidic silane, Me2SiHCl, can mediate the direct cross-coupling of a wide range of carbonyl compounds with alcohols to form dialkyl ethers. The reaction is operationally simple, tolerates a range of polar functional groups, can be utilized to make sterically hindered ethers, and is extendable to sulfur and nitrogen nucleo­philes.


Catalysts ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 8
Author(s):  
Hui-Ju Chen ◽  
Chien-Cheng Chiu ◽  
Tsui Wang ◽  
Dong-Sheng Lee ◽  
Ta-Jung Lu

The bis-NHC–Ag/Pd(OAc)2 catalytic system (NHC = N-heterocyclic carbene), a combination of bis-NHC–Ag complex and Pd(OAc)2, was found to be a smart catalyst in the Pd-catalyzed transfer hydrogenation of various functionalized arenes and internal/terminal alkynes. The catalytic system demonstrated high efficiency for the reduction of a wide range of various functional groups such as carbonyls, alkynes, olefins, and nitro groups in good to excellent yields and high chemoselectivity for the reduction of functional groups. In addition, the protocol was successfully exploited to stereoselectivity for the transformation of alkynes to alkenes in aqueous media under air. This methodology successfully provided an alternative useful protocol for reducing various functional groups and a simple operational protocol for transfer hydrogenation.


Materials ◽  
2022 ◽  
Vol 15 (2) ◽  
pp. 466
Author(s):  
Kaixin Chang ◽  
Qianjin Zhu ◽  
Liyan Qi ◽  
Mingwei Guo ◽  
Woming Gao ◽  
...  

Nitrogen-doped carbon quantum dots (N-CQDs) were synthesized in a one-step hydrothermal technique utilizing L-lactic acid as that of the source of carbon and ethylenediamine as that of the source of nitrogen, and were characterized using dynamic light scattering, X-ray photoelectron spectroscopy ultraviolet-visible spectrum, Fourier-transformed infrared spectrum, high-resolution transmission electron microscopy, and fluorescence spectrum. The generated N-CQDs have a spherical structure and overall diameters ranging from 1–4 nm, and their surface comprises specific functional groups such as amino, carboxyl, and hydroxyl, resulting in greater water solubility and fluorescence. The quantum yield of N-CQDs (being 46%) is significantly higher than that of the CQDs synthesized from other biomass in literatures. Its fluorescence intensity is dependent on the excitation wavelength, and N-CQDs release blue light at 365 nm under ultraviolet light. The pH values may impact the protonation of N-CQDs surface functional groups and lead to significant fluorescence quenching of N-CQDs. Therefore, the fluorescence intensity of N-CQDs is the highest at pH 7.0, but it decreases with pH as pH values being either more than or less than pH 7.0. The N-CQDs exhibit high sensitivity to Fe3+ ions, for Fe3+ ions would decrease the fluorescence intensity of N-CQDs by 99.6%, and the influence of Fe3+ ions on N-CQDs fluorescence quenching is slightly affected by other metal ions. Moreover, the fluorescence quenching efficiency of Fe3+ ions displays an obvious linear relationship to Fe3+ concentrations in a wide range of concentrations (up to 200 µM) and with a detection limit of 1.89 µM. Therefore, the generated N-CQDs may be utilized as a robust fluorescence sensor for detecting pH and Fe3+ ions.


2020 ◽  
Author(s):  
Hojoon Park ◽  
jin-quan yu

<div>Cycloaddition reactions provide an expeditious route to construct ring systems in a highly convergent and stereoselective manner. For a typical cycloaddition reaction to occur, however, the installation of multiple reactive functional groups (π-bonds, leaving group, etc.) are required within the substrates, compromising the overall efficiency or scope of the cycloaddition reaction. Here, we report a palladium-catalyzed [3+2] reaction that utilizes C(sp<sup>3</sup>)–H activation to generate the three-carbon unit for formal cycloaddition with maleimides. We implemented a strategy where the initial C(sp<sup>3</sup>)–H activation/olefin insertion would trigger a relayed, second remote C(sp<sup>3</sup>)–H activation to complete a formal [3+2] cycloaddition. The diastereoselectivity profile of this reaction resembles that of a typical pericyclic cycloaddition reaction in that the relationships between multiple stereocenters are exquisitely controlled in a single reaction. The key to success was the use of weakly coordinating amides as the directing group, as undesired Heck or alkylation pathways were preferred with other types of directing groups. The use of the pyridine-3-sulfonic acid ligands is critical to enable C(sp<sup>3</sup>)–H activation directed by this weak coordination. The method is compatible with a wide range of amide substrates, including lactams, which lead to novel spiro-bicyclic products. The [3+2] product is also shown to undergo a reductive desymmetrization process to access chiral cyclopentane bearing multiple stereocenters with excellent enantioselectivity.</div>


Author(s):  
Marta Olivares ◽  
Martin Albrecht

Pyridyl-triazolylidene ligands with variable donor properties were used as tunable ligands at a dihydride iridium(III) center. The straightforward synthesis of this type of ligand allows for an easy incorporation of electron donating substituents in different positions of the pyridine ring or different functional groups such as esters, alkoxy or aliphatic chains on the C4 position of the triazole heterocycle. The stability of these hydride metal systems allowed these complexes to be used as models for studying the influence of the ligand modifications on hydride reactivity. Spectroscopic analysis provided unambiguous structural assignment of the dihydride system. Modulation of the electronic properties of the wingtip substituents did not appreciably alter the reactivity of the hydrides. Reactivity studies using acids with a wide range of pKa values indicated a correlation between hydride reactivity and acidity and showed exclusive reactivity towards the less shielded hydride trans to the carbene carbon rather than the more shielded hydride trans to the pyridine ring, suggesting that the trans effect is more relevant in these reactions than the NMR spectroscopically deduced hydridic character.


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