Selective and scalable electrosynthesis of 2H-2-(aryl)-benzo[d]-1,2,3-triazoles and their N-oxides by using leaded bronze cathodes

Electrosynthesis of 2H-2-(aryl)benzo[d]-1,2,3-triazoles and their N-oxides from 2-nitroazobenzene derivatives is reported. The electrolysis is conducted in a very simple undivided cell under constant current conditions with a leaded bronze cathode and a glassy carbon anode. The product distribution between 2H-2-(aryl)benzo[d]-1,2,3-triazoles and their N-oxides can be guided by simply controlling the current density and the amount of the charge applied. The reaction tolerates several sensitive functional groups in reductive electrochemistry. The usefulness and the applicability of the synthetic method is demonstrated by a formal synthesis of an antiviral compound

Tetramethylammonium Fluoride : Fundamental Properties and Applications in C-F Bond-Forming Reactions and as a Base

Nucleophilic ionic sources of fluoride are essential reagents in the synthetic toolbox to access high added-value fluorinated building blocks unattainable by other means. In this review, we provide a concise description and rationale of the outstanding features of one of these reagents, tetramethylammonium fluoride (TMAF), as well as disclosing the different methods for its preparation, and how its physicochemical properties and solvation effects in different solvents are intimately associated with its reactivity. Furthermore, herein we also comprehensively describe its historic and recent utilization, up to December 2021, in C-F bond-forming reactions with special emphasis on nucleophilic aromatic substitution fluorinations with a potential sustainable application in industrial settings, as well as its use as a base capable of rendering unprecedented transformations. Keywords: tetramethylammonium fluoride; TMAF; solvation effects; nucleophilic fluorination; sustainable industrial fluorination; SNAr; [18F]-radiolabelling; superbases; selective methylation; fluorinated excited speciesPeer reviewe

Tetramethylammonium Fluoride : Fundamental Properties and Applications in C-F Bond-Forming Reactions and as a Base

Nucleophilic ionic sources of fluoride are essential reagents in the synthetic toolbox to access high added-value fluorinated building blocks unattainable by other means. In this review, we provide a concise description and rationale of the outstanding features of one of these reagents, tetramethylammonium fluoride (TMAF), as well as disclosing the different methods for its preparation, and how its physicochemical properties and solvation effects in different solvents are intimately associated with its reactivity. Furthermore, herein we also comprehensively describe its historic and recent utilization, up to December 2021, in C-F bond-forming reactions with special emphasis on nucleophilic aromatic substitution fluorinations with a potential sustainable application in industrial settings, as well as its use as a base capable of rendering unprecedented transformations. Keywords: tetramethylammonium fluoride; TMAF; solvation effects; nucleophilic fluorination; sustainable industrial fluorination; SNAr; [18F]-radiolabelling; superbases; selective methylation; fluorinated excited speciesPeer reviewe

Direct electrochemical synthesis of 2,3-disubstituted quinoline N-oxides by cathodic reduction of nitro arenes

The use of electric current in synthetic organic chemistry offers a sustainable tool for the selective reductive synthesis of quinoline N-oxides starting from easily accessible nitro compounds. The reported method employs mild and reagent-free conditions, a simple undivided cell, and constant current electrolysis set-up which provides conversion with a high atom economy. The synthesis of 30 differently substituted quinoline N-oxides was successfully performed in up to 90 % yield. Using CV studies, the mechanism of the selective formation of the quinoline N-oxides was elucidated. The technical relevance of the described reaction could be shown in a 50-fold scale-up reaction

Carbocatalytic Oxidative Dehydrogenative Couplings of (Hetero)Aryls by Oxidized Multi‐Walled Carbon Nanotubes in Liquid Phase

HNO3-oxidized carbon nanotubes catalyze oxidative dehydrogenative (ODH) carbon-carbon bond formation between electron-rich (hetero)aryls with O-2 as a terminal oxidant. The recyclable carbocatalytic method provides a convenient and an operationally easy synthetic protocol for accessing various benzofused homodimers, biaryls, triphenylenes, and related benzofused heteroaryls that are highly useful frameworks for material chemistry applications. Carbonyls/quinones are the catalytically active site of the carbocatalyst as indicated by model compounds and titration experiments. Further investigations of the reaction mechanism with a combination of experimental and DFT methods support the competing nature of acid-catalyzed and radical cationic ODHs, and indicate that both mechanisms operate with the current material.Peer reviewe

Carbocatalytic Cascade Synthesis of Polysubstituted Quinolines from Aldehydes and 2-Vinyl Anilines

Oxidized active carbon (oAC) catalyses the formation of polysubstituted quinolines from o-vinyl anilines and aldehydes. The reaction proceeds in a cascade manner through condensation, electrocyclization and dehydrogenation, and gives access to a wide range of quinolines with alkyl and/or aryl substituents as demonstrated with 40 examples. The metal-free catalytic procedure allows a heterogeneous protocol for the synthesis of various polysubstituted quinolines. The mechanistic studies imply that both the acid and quinoidic groups in oAC are integral for the catalytic manifold.Peer reviewe

Validation of 34betaE12 immunoexpression in clear cell papillary renal cell carcinoma as a sensitive biomarker

Clear cell papillary renal cell carcinoma (CCPRCC) is a recently recognised neoplasm with a broad spectrum of morphological characteristics, thus representing a challenging differential diagnosis, especially with the low malignant potential multicystic renal cell neoplasms and clear cell renal cell carcinoma. We selected 14 cases of CCPRCC with a wide spectrum of morphological features diagnosed on morphology and CK7 immunoreactivity and analysed them using a panel of immunohistochemical markers, focusing on 34 beta E12 and related CKs 1,5,10 and 14 and several molecular analyses such as fluorescence in situ hybridisation (FISH), array comparative genomic hybridisation (aCGH), VHL methylation, VHL and TCEB1 sequencing and multiplex ligation-dependent probe amplification (MLPA). Twelve of 13 (92%) CCPRCC tumours were positive for 34 beta E12. One tumour without 3p alteration by FISH revealed VHL mutation and 3p deletion at aCGH; thus, it was re-classified as clear cell RCC. We concluded that: (1) immunohistochemical expression of CK7 is necessary for diagnostic purposes, but may not be sufficient to identify CCPRCC, while 34 beta E12, in part due to the presence of CK14 antigen expression, can be extremely useful for the recognition of this tumour; and (2) further molecular analysis of chromosome 3p should be considered to support of CCPRCC diagnosis, when FISH analysis does not evidence the common loss of chromosome 3p.Peer reviewe

Carbon dioxide use and removal : Prospects and policies

This report presents an overview of the current status of carbon capture, utilisation and storage (CCUS) and carbon dioxide removal (CDR), in terms of and main technologies, markets and policies, especially from the perspective of Finland. CDR refers to technologies and practices, which can remove carbon dioxide (CO2) from the atmosphere and store it in a manner intended to be permanent. CCUS refers to permanent storage of captured CO2 or to the utilisation of captured CO2 as a feedstock for different products which also form short- or long-term storage over their life cycle. The products can range from fuels (short lifetime) to performance polymers (long lifetime) and to mineral products (often permanent storage). The market assessment included also quantitative and qualitative estimates for future development in size and growing CCUS and CDR solutions. Finland’s export potential in the technologies and products was also investigated. The policy environment of the technologies was assessed in terms of greenhouse gas accounting and reporting rules under the UNFCC and EU legal frameworks. Moreover, an international benchmarking of national policies was carried out to survey good practices in peer jurisdictions. Taking note of the assessed main technology options, the policy overview was used to identify policy development needs and to provide recommendations accordingly.This publication is part of the implementation of the Government Plan for Analysis, Assessment and Research. (tietokayttoon.fi) The content is the responsibility of the producers of the information and does not necessarily represent the view of the Government

Carbon Materials as Catalytic Tools for Oxidative Dehydrogenations and Couplings in Liquid Phase

Carbocatalysis is a heterogeneous metal-free catalytic technique of high potential for current and future synthetic processes. Carbocatalysts entail heterogeneous materials based on sp2/sp3 interconnected carbons decorated with oxygen functional groups, defects, and other heteroatom dopants. In this review, we cover a wide range of different carbocatalyzed oxidative dehydrogenation reactions particularly emphasizing on liquid phase transformations that are relevant for synthetic organic chemists.Carbocatalysis is a heterogeneous metal-free catalytic technique of high potential for current and future synthetic processes. Carbocatalysts entail heterogeneous materials based on sp(2)/sp(3) interconnected carbons decorated with oxygen functional groups, defects, and other heteroatom dopants. In this short review, we cover a wide range of different carbocatalyzed oxidative dehydrogenation reactions, with particular emphasis on liquid-phase transformations that are relevant for synthetic organic chemists.1 Introduction2 Structures of Catalytic Carbon Materials3 Oxidative Aromatizations with Activated Carbon4 Oxidative Dehydrogenation CH-CH Couplings5 Oxidative Dehydrogenation Coupling of Benzyl Amines6 Oxidations of Alcohols7 Other Oxidative Transformations by Heteroatom-Doped Carbon Materials8 Asphaltene Oxide9 Conclusions and OutlookPeer reviewe

Quinones as Redox Mediators

The research of this thesis was initiated when we made an unexpected discovery that a carbon support of a heterogeneous catalyst, which was assumed to be inert, was capable of oxidatively coupling indoles. We later showed, that carbonyls / quinones were formed on the carbon that could act as a redox mediator for this reaction. The results of this work are based on three peer-reviewed publications. In publications I and II, the oxidative power of heterogeneous quinones is established and harnessed for the synthesis of new carbon-carbon sp2 bonds between two organic molecules. In the third publication, this discovered reactivity is transferred to homogeneous conditions. In this research, both heterogeneous and homogeneous quinones were used. Although the underlying chemistry between them is similar, they still form two different conceptual entities and therefore the discussion is also divided into two separate parts: homogeneous and heterogeneous quinones. As this thesis and other publications have shown, heterogenous and homogeneous quinone-mediated reactions can be interconnected. Therefore, the scientific importance of this dissertation is not in the different kinds of organic transformations per se, but in showing that the transformations are accessible with the both heterogeneous and homogeneous quinones.Tässä väitöskirjatyössä tutkittiin niin kutsuttujen kinonien käyttöä hapetus-pelkistysreaktioiden välittäjinä. Tutkimus alkoi, kun havaitsimme yllättäen erään heterogeenisen kultakatalyytin hapettavan indoleita dimeereiksi. Kultakatalyytti valmistettiin hapettavissa olosuhteissa, jolloin katalyytin kantajana käytettyyn hiileen syntyi karbonyyli / kinoni -ryhmiä, jotka katalysoivat indolien välisen reaktion. Artikkeliväitöskirjan ensimmäisessä osajulkaisussa löysimme uuden reaktiivisuuden. Toisessa osajulkaisussa sekä karakterisoimme toiminallisen ryhmän karbonyyleiksi / kinoneiksi että laajensimme reaktion laajuutta. Osajulkaisussa kolme siirsimme reaktiivisuuden homogeenisiin olosuhteisiin vaihtamalla kinonivälittäjän heterogeenisestä hiilipohjaisesta kinonista 2,3-dikloro-5,6-disyano-1,4-bentsokinoniin. Lisäksi sovelsimme synteesimenetelmäämme luonnonaine shandougenine B:n synteesiin. Väitöskirjan yhteenveto-osan kirjallisuustarkastelun tarkoituksena on välittää lukijalle kuva sekä homogeenisten kinonien hapetus-pelkistyskemiasta että heterogeenisten kinonien valmistuksesta ja karakterisoinnista. Tämän lisäksi väitöskirjassa esitellään homogeenisten ja heterogeenisten kinonien välittämiä orgaanisia reaktioita