scholarly journals Vinyl Sulfoxonium Ylide: A New Vinyl Carbenoid Transfer Reagent for the Synthesis of Heterocycles

Synlett ◽  
2019 ◽  
Vol 30 (12) ◽  
pp. 1377-1383 ◽  
Author(s):  
Janakiram Vaitla ◽  
Annette Bayer ◽  
Kathrin H. Hopmann
Keyword(s):  
Transfer Reactions ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
The Stability

Sulfoxonium ylides have recently gained prominence as safe carbenoid precursors in metal-catalyzed reactions. The stability and reactivity of sulfoxonium ylides depend on the substitution of the ylide carbon. The reactivity of vinyl-substituted sulfoxonium ylides is different and offers several advantages over known stabilized sulfoxonium ylides in the case of carbenoid transfer reactions. Herein, we provide an overview of early efforts in this area, with particular emphasis on our own recent development of sulfoxonium ylide-derived vinyl carbenoid transformations for N-Heterocycles.1 Introduction2 Classification of Sulfoxonium Ylides3 Synthesis of Vinyl Sulfoxonium Ylides4 [3+2] Annulation of Vinyl Sulfoxonium Ylides5 [4+1] Annulation of Vinyl Sulfoxonium Ylides6 Conclusion

Catalytic Enantioselective Benzylation Directly from Aryl Acetic Acids

2018 ◽  
Author(s):  
Patrick Moon ◽  
Zhongyu Wie ◽  
Rylan Lundgren
Keyword(s):  
Functional Group ◽  
Terminal Event ◽  
Radical Intermediates ◽  
Carbon Carbon Bond ◽  
Or Groups ◽  
Reaction Proceeds ◽  
Wide Availability ◽  
Metal Catalyzed ◽  
The Stability ◽  
Acetic Acids

The stability and wide availability of carboxylic acids make them valuable reagents in chemical synthesis. Most transition metal catalyzed processes using carboxylic acid substrates are initiated by a decarboxylation event that generates reactive carbanion or radical intermediates. Developing enantioselective methodologies relying on these principles can be challenging, as highly reactive species tend to react indiscriminately without selectivity. Furthermore, anionic or radical intermediates generated from decarboxylation can be incompatible with protic and electrophilic functionality, or groups that undergo trapping with radicals. We demonstrate that metal-catalyzed enantioselective benzylation reactions of allylic electrophiles can occur directly from aryl acetic acids. The reaction proceeds via a pathway in which decarboxylation is the terminal event, occurring after stereoselective carbon–carbon bond formation. The mechanistic features of the process enable enantioselective benzylation without the generation of a highly basic nucleophile. Thus, the process has broad functional group compatibility that would not be possible employing established protocols.<br>

Influence of internal and external risks on sustainability of financial system of Аltai krai

2018 ◽  
Vol 35 (4) ◽  
pp. 133-136
Author(s):  
R. N. Ibragimov
Keyword(s):  
Sustainable Development ◽  
Financial Stability ◽  
Management Strategy ◽  
Financial System ◽  
Risk Management Strategy ◽  
The Sustainable Development ◽  
The Stability ◽  
The Impact

The article examines the impact of internal and external risks on the stability of the financial system of the Altai Territory. Classification of internal and external risks of decline, affecting the sustainable development of the financial system, is presented. A risk management strategy is proposed that will allow monitoring of risks, thereby these measures will help reduce the loss of financial stability and ensure the long-term development of the economy of the region.

DEVELOPMENT OF THE BASIC CRITERIA FOR RUSSIAN COASTS TYPIFICATION

2017 ◽  
Author(s):  
Рубен Косян ◽  
Ruben Kosyan ◽  
Viacheslav Krylenko ◽  
Viacheslav Krylenko
Keyword(s):  
Coastal Zone ◽  
Coastal Area ◽  
Economic Activity ◽  
Basic Information ◽  
Dynamic Features ◽  
Static State ◽  
Evolutionary Features ◽  
Coastal Features ◽  
The Stability

There are many types of coasts classifications that indicate main coastal features. As a rule, the "static" state of the coasts is considered regardless of their evolutionary features and ways to further transformation. Since the most part of the coastal zone studies aimed at ensuring of economic activity, it is clear that the classification of coast types should indicate total information required by the users. Accordingly, the coast classification should include the criterion, characterizing as dynamic features of the coast and the conditions and opportunities of economic activity. The coast classification, of course, should be based on geomorphological coast typification. Similar typification has been developed by leading scientists from Russia and can be used with minimal modifications. The authors propose to add to basic information (geomorphological type of coast) the evaluative part for each coast sector. It will include the estimation of the coast changes probability and the complexity of the coast stabilization for economic activity. This method will allow to assess the dynamics of specific coastal sections and the processes intensity and, as a result – the stability of the coastal area.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Chemistry of Unsymmetrical C1-Substituted Oxabenzonorbornadienes

2021 ◽  
Vol 17 ◽  
Author(s):  
Austin Pounder ◽  
Angel Ho ◽  
Matthew Macleod ◽  
William Tam
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Substituent Effects ◽  
Face Selectivity ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Synthetic Intermediate

: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate which can be readily activated by transition metal complexes with great face selectivity due to its dual-faced nature and intrinsic angle strain on the alkene. To date, the understanding of transition-metal catalyzed reactions of OBD itself has burgeoned; however, this has not been the case for unsymmetrical OBDs. Throughout the development of these reactions, the nature of C1-substituent has proven to have a profound effect on both the reactivity and selectivity of the outcome of the reaction. Upon substitution, different modes of reactivity arise, contributing to the possibility of multiple stereo-, regio-, and in extreme cases, constitutional isomers which can provide unique means of constructing a variety of synthetically useful cyclic frameworks. To maximize selectivity, an understanding of bridgehead substituent effects is crucial. To that end, this review outlines hitherto reported examples of bridgehead substituent effects on the chemistry of unsymmetrical C1-substituted OBDs.

scholarly journals Can Vaccination Trigger Autoimmune Disorders? A Meta-Analysis

Vaccines ◽  
2021 ◽  
Vol 9 (8) ◽  
pp. 821
Author(s):  
Marek Petráš ◽  
Ivana Králová Lesná ◽  
Jana Dáňová ◽  
Alexander M. Čelko
Keyword(s):  
Meta Analysis ◽  
Autoimmune Disorders ◽  
Risk Of Bias ◽  
Extensive Literature ◽  
Primary Analysis ◽  
Measures Of Association ◽  
Assessment Development ◽  
Extensive Literature Search ◽  
The Stability

Vaccination as an important tool in the fight against infections has been suggested as a possible trigger of autoimmunity over the last decades. To confirm or refute this assumption, a Meta-analysis of Autoimmune Disorders Association With Immunization (MADAWI) was conducted. Included in the meta-analysis were a total of 144 studies published in 1968–2019 that were available in six databases and identified by an extensive literature search conducted on 30 November 2019. The risk of bias classification of the studies was performed using the Newcastle–Ottawa Quality Assessment Scale. The strength of evidence was assessed using the Grading of Recommendations Assessment, Development, and Evaluation. While our primary analysis was conducted in terms of measures of association employed in studies with a low risk of bias, the robustness of the MADAWI outcome was tested using measures independent of each study risk of bias. Additionally, subgroup analyses were performed to determine the stability of the outcome. The pooled association of 0.99 (95% confidence interval, 0.97–1.02), based on a total of 364 published estimates, confirmed an equivalent occurrence of autoimmune disorders in vaccinated and unvaccinated persons. The same level of association reported by studies independently of the risk of bias was supported by a sufficient number of studies, and no serious limitation, inconsistency, indirectness, imprecision, and publication bias. A sensitivity analysis did not reveal any discrepancy in the primary result. Current common vaccination is not the cause of any of the examined autoimmune disorders in the medium and long terms.

scholarly journals Transition metal-catalyzed reactions of N-sulfinyl imines

2021 ◽  
pp. 153104
Author(s):  
Francisco Foubelo ◽  
Carmen Nájera ◽  
José M. Sansano ◽  
Miguel Yus
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

scholarly journals An Ensemble Feature Selection Approach to Identify Relevant Features from EEG Signals

2021 ◽  
Vol 11 (15) ◽  
pp. 6983
Author(s):  
Maritza Mera-Gaona ◽  
Diego M. López ◽  
Rubiel Vargas-Canas
Keyword(s):  
Feature Selection ◽  
Sensitivity And Specificity ◽  
Eeg Signals ◽  
Specificity And Sensitivity ◽  
Selection Approach ◽  
Feature Selection Approach ◽  
The Stability ◽  
Selection Algorithms ◽  
Epileptiform Events

Identifying relevant data to support the automatic analysis of electroencephalograms (EEG) has become a challenge. Although there are many proposals to support the diagnosis of neurological pathologies, the current challenge is to improve the reliability of the tools to classify or detect abnormalities. In this study, we used an ensemble feature selection approach to integrate the advantages of several feature selection algorithms to improve the identification of the characteristics with high power of differentiation in the classification of normal and abnormal EEG signals. Discrimination was evaluated using several classifiers, i.e., decision tree, logistic regression, random forest, and Support Vecctor Machine (SVM); furthermore, performance was assessed by accuracy, specificity, and sensitivity metrics. The evaluation results showed that Ensemble Feature Selection (EFS) is a helpful tool to select relevant features from the EEGs. Thus, the stability calculated for the EFS method proposed was almost perfect in most of the cases evaluated. Moreover, the assessed classifiers evidenced that the models improved in performance when trained with the EFS approach’s features. In addition, the classifier of epileptiform events built using the features selected by the EFS method achieved an accuracy, sensitivity, and specificity of 97.64%, 96.78%, and 97.95%, respectively; finally, the stability of the EFS method evidenced a reliable subset of relevant features. Moreover, the accuracy, sensitivity, and specificity of the EEG detector are equal to or greater than the values reported in the literature.

scholarly journals Chiral Aziridine Sulfide N(sp3),S-Ligands for Metal-Catalyzed Asymmetric Reactions

Symmetry ◽  
2021 ◽  
Vol 13 (3) ◽  
pp. 502
Author(s):  
Agata J. Pacuła-Miszewska ◽  
Anna Laskowska ◽  
Anna Kmieciak ◽  
Mariola Zielińska-Błajet ◽  
Marek P. Krzemiński ◽  
...  
Keyword(s):  
Metal Binding ◽  
Electronic Effect ◽  
Asymmetric Reactions ◽  
Addition Reactions ◽  
Phenyl Sulfide ◽  
Enantiomeric Ratio ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Sulfide Group

A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide group—was synthesized and evaluated in the Pd-catalyzed Tsuji–Trost reaction and addition of diethylzinc and phenylethynylzinc to benzaldehyde. A high enantiomeric ratio for the addition reactions (up to 94.2:5.8) was obtained using the aziridine ligand bearing a p-nitro phenyl sulfide group. Collected results reveal a specific electronic effect that, by the presence of particular electron-donating or electron-withdrawing groups in the PhS- moiety, influences the σ-donor–metal binding and the enantioselectivity of the catalyzed reactions.

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