scholarly journals Selective Functionalization of the 1H-Imidazo[1,2-b]pyrazole Scaffold. A new Potential Non-classical Isostere of Indole and a Precursor of Push-Pull Dyes

2021 ◽  
Author(s):  
Kuno Schwärzer ◽  
Saroj K. Rout ◽  
Derya Bessinger ◽  
Fabio Lima ◽  
Cara Emily Brocklehurst ◽  
...  

We report the full selective functionalization of the 1H-imidazo[1,2-b]pyrazole scaffold using a Br/Mg-exchange, as well as regioselective magnesiations and zincations with TMP-bases (TMP = 2,2,6,6-tetramethylpiperidyl), followed by trapping reactions with...

2010 ◽  
Vol 38 (1) ◽  
pp. 80-98 ◽  
Author(s):  
M. Gerster ◽  
C. Fagouri ◽  
E. Peregi

Abstract One challenge facing green tire technology is to achieve good silica hydrophobation/dispersion within the polymer matrix without a detrimental increase in the rubber compound’s viscosity during compounding. This phenomenon is well known to be induced by premature and unwanted coupling and/or crosslinking of the traditional coupling agents. The current state-of-the-art polysulfides silanes, bis(3-triethoxysilylpropyl)tetrasulfide and to a lesser extent bis(3-triethoxysilylpropyl)disulfide (“Product Application—VP Si 75/VP X 75-S in the Rubber Industry,” Degussa Hüls Report No. PA 723.1E), need to be carefully incorporated with careful temperature control during the rubber compounding to prevent this “scorchy” behavior. This paper will present novel monofunctional silanes which are suited for preparing highly silica-loaded rubber compounds of superior processability, while applying fewer mixing passes, thereby reducing mixing times which can lead to improved productivity and cost savings. Additionally, these safer coupling agents can be processed at higher temperatures which can, again, lead to reduced mixing time and better ethanol removal thereby improving the tire’s physical properties and reducing the volatile organic compounds generated during the tire’s use. The rubber compounds produced using these monofunctional silanes are characterized by lower Mooney viscosity and improved processability. Advantageously, within these novel chemical classes of coupling agents, selective functionalization of the silanes allows production of tailor-made coupling agents which can respond to the specific requirements of the tire industry (Vilgis, T. A. and Heinrich, G., “Die Physic des Autoreifens,” Physikalische Blätter, Vol. 57, 2001, pp. 1–7).


2019 ◽  
Author(s):  
Sandeep Pimparkar ◽  
Trisha Bhattacharya ◽  
Arun Maji ◽  
Argha Saha ◽  
Ramasamy Jayarajan ◽  
...  

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the <i>para</i>-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of <i>para</i>-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications


2019 ◽  
Author(s):  
Sandeep Pimparkar ◽  
Trisha Bhattacharya ◽  
Arun Maji ◽  
Argha Saha ◽  
Ramasamy Jayarajan ◽  
...  

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the <i>para</i>-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of <i>para</i>-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications


2020 ◽  
Author(s):  
Bapurao Bhoge ◽  
Ishu Saraogi

Chemo- and site-specific modifications in oligonucleotides have wide applicability as mechanistic probes in chemical biology. Here we have employed a classical reaction in organic chemistry, reductive amination, to selectively functionalize the N<sup>2</sup>-amine of guanine/2’-deoxyguanine monophosphate. This method specifically modifies guanine in several tested DNA oligonucleotides, while leaving the other bases unaffected. Using this approach, we have successfully incorporated desired handles chemoselectively into DNA oligomers.


2021 ◽  
Author(s):  
Mathias O. Senge ◽  
Natalia N. Sergeeva ◽  
Karl J. Hale

The development of porphyrin synthesis is illustrated, using classic and modern-day examples, which attempt to provide insights, including mechanistic ones, into the most used methods for porphyrin ring-construction and selective functionalization.


RSC Advances ◽  
2021 ◽  
Vol 11 (34) ◽  
pp. 20859-20864
Author(s):  
Pramodkumar D. Jadhav ◽  
Jianheng Shen ◽  
Peta-Gaye Burnett ◽  
Jian Yang ◽  
Ramaswami Sammynaiken ◽  
...  

One step regioselective methionine epimerization in cyclic peptides followed by selective functionalization leads to chemical novelty.


Synthesis ◽  
2020 ◽  
Vol 52 (17) ◽  
pp. 2483-2496
Author(s):  
Johannes F. Teichert ◽  
Lea T. Brechmann

The key reactive intermediate of copper(I)-catalyzed alkyne semihydrogenations is a vinylcopper(I) complex. This intermediate can be exploited as a starting point for a variety of trapping reactions. In this manner, an alkyne semihydrogenation can be turned into a dihydrogen­-mediated coupling reaction. Therefore, the development of copper-catalyzed (transfer) hydrogenation reactions is closely intertwined with the corresponding reductive trapping reactions. This short review highlights and conceptualizes the results in this area so far, with H2-mediated carbon–carbon and carbon–heteroatom bond-forming reactions emerging under both a transfer hydrogenation setting as well as with the direct use of H2. In all cases, highly selective catalysts are required that give rise to atom-economic multicomponent coupling reactions with rapidly rising molecular complexity. The coupling reactions are put into perspective by presenting the corresponding (transfer) hydrogenation processes first.1 Introduction: H2-Mediated C–C Bond-Forming Reactions2 Accessing Copper(I) Hydride Complexes as Key Reagents for Coupling Reactions; Requirements for Successful Trapping Reactions 3 Homogeneous Copper-Catalyzed Transfer Hydrogenations4 Trapping of Reactive Intermediates of Alkyne Transfer Semi­hydrogenation Reactions: First Steps Towards Hydrogenative Alkyne Functionalizations 5 Copper(I)-Catalyzed Alkyne Semihydrogenations6 Copper(I)-Catalyzed H2-Mediated Alkyne Functionalizations; Trapping of Reactive Intermediates from Catalytic Hydrogenations6.1 A Detour: Copper(I)-Catalyzed Allylic Reductions, Catalytic Generation of Hydride Nucleophiles from H2 6.2 Trapping with Allylic Electrophiles: A Copper(I)-Catalyzed Hydro­allylation Reaction of Alkynes 6.3 Trapping with Aryl Iodides7 Conclusion


ACS Nano ◽  
2012 ◽  
Vol 6 (10) ◽  
pp. 9214-9220 ◽  
Author(s):  
Winand Slingenbergh ◽  
Sanne K. de Boer ◽  
Thorben Cordes ◽  
Wesley R. Browne ◽  
Ben L. Feringa ◽  
...  

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