scholarly journals Bipolar Electrochemical Measurement of Enantiomeric Excess with Inherently Chiral Polymer Actuators

Author(s):  
Serena Arnaboldi ◽  
Gerardo Salinas ◽  
Giorgia Bonetti ◽  
Roberto Cirilli ◽  
Tiziana Benincori ◽  
...  
2020 ◽  
Author(s):  
Tomas Hardwick ◽  
Rossana Cicala ◽  
Nisar Ahmed

<p>Many chiral compounds have become of great interest to the pharmaceutical industry as they possess various biological activities. Concurrently, the concept of “memory of chirality” has been proven as a powerful tool in asymmetric synthesis, while flow chemistry has begun its rise as a new enabling technology to add to the ever increasing arsenal of techniques available to the modern day chemist. Here, we have employed a new simple electrochemical microreactor design to oxidise an L-proline derivative at room temperature in continuous flow. Flow performed in microreactors offers up a number of benefits allowing reactions to be performed in a more convenient and safer manner, and even allow electrochemical reactions to take place without a supporting electrolyte due to a very short interelectrode distance. By the comparison of electrochemical oxidations in batch and flow we have found that continuous flow is able to outperform its batch counterpart, producing a good yield (71%) and a better enantiomeric excess (64%) than batch with a 98% conversion. We have, therefore, provided evidence that continuous flow chemistry has the potential to act as a new enabling technology to replace some aspects of conventional batch processes. </p>


2019 ◽  
Author(s):  
John Montgomery ◽  
Alexander W. Rand

A new method to access alpha-arylated benzamides has been enabled by metallaphotoredox catalysis. This system allows for non-directed C–H functionalization of N-alkyl benzamides using a dual nickel/iridium catalytic system to form tertiary stereocenters in good enantiomeric excess and moderate yields. This reaction shows excellent functional group compatibility and can be performed using a number of sterically and electronically different aryl bromides and secondary benzamides.


2019 ◽  
Author(s):  
John Montgomery ◽  
Alexander W. Rand

A new method to access alpha-arylated benzamides has been enabled by metallaphotoredox catalysis. This system allows for non-directed C–H functionalization of N-alkyl benzamides using a dual nickel/iridium catalytic system to form tertiary stereocenters in good enantiomeric excess and moderate yields. This reaction shows excellent functional group compatibility and can be performed using a number of sterically and electronically different aryl bromides and secondary benzamides.


Author(s):  
Karam Asad ◽  
Anastasios Stergiou ◽  
Andreas Kourtellaris ◽  
Nikos Tagmatarchis ◽  
Nikos Chronakis
Keyword(s):  

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1165
Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2′-bis(aminomethyl)-1,1′-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = η5–C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.


Sensors ◽  
2021 ◽  
Vol 21 (5) ◽  
pp. 1659
Author(s):  
Nutcha Larpant ◽  
Pramod K. Kalambate ◽  
Tautgirdas Ruzgas ◽  
Wanida Laiwattanapaisal

This paper proposes a combined strategy of using paper-based competitive immunochromatography and a near field communication (NFC) tag for wireless cotinine determination. The glucose oxidase labeled cotinine antibody specifically binds free cotinine in a sample, whereas the unoccupied antibody attached to BSA-cotinine at the test line on a lateral flow strip. The glucose oxidase on the strip and an assistant pad in the presence of glucose generated H2O2 and imposed the Ag oxidation on the modified electrode. This enabled monitoring of immunoreaction by either electrochemical measurement or wireless detection. Wireless sensing was realized for cotinine in the range of 100–1000 ng/mL (R2 = 0.96) in PBS medium. Undiluted urine samples from non-smokers exhibited an Ag-oxidation rate three times higher than the smoker’s urine samples. For 1:8 diluted urine samples (smokers), the proposed paper-based competitive immunochromatography coupled with an enzyme-modified electrode differentiated positive and negative samples and exhibited cotinine discrimination at levels higher than 12 ng/mL. This novel sensing platform can potentially be combined with a smartphone as a reader unit.


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