A range of hitherto unexplored biomass‐derived chemicals have been evaluated as new sustainable solvents for a large variety of CO₂‐based carboxylation reactions. Known biomass‐derived solvents (biosolvents) are also included in the study and the results are compared with commonly used solvents for the reactions. Biosolvents can be efficiently applied in a variety of carboxylation reactions, ...

We present an extensive analysis of one- and two-photon absorption processes in some organic host-guest (H-G) complexes using linear and quadratic response theory within the framework of time-dependent density functional theory. For this purpose, we have considered all possible 20 host-guest complexes constructed from 4 host and 5 guest molecules. We have analysed how the one- and two-photon activity ...

The cellular methyl donor S-adenosylmethionine (SAM) and other endo/exogenous agents methylate DNA bases non-enzymatically into products interfering with replication and transcription. An important product is 3-methyladenine (m³A), which in <i>Escherichia coli</i> is removed by m³A-DNA glycosylase I (Tag) and II (AlkA). The <i>tag</i> gene is constitutively expressed, while ...

A set of rhenium(V)-oxo <i>meso</i>-triarylcorroles bearing ester and carboxylic acid functionalities were synthesized with a view to determining their potential for photodynamic therapy. Toward this end, we measured their near-IR phosphorescence and their ability to sensitize singlet oxygen formation. The two esters studied, Re^VO 5,10,15-tris(<i>meta</i>-carbomethoxyphenyl)corrole and ...

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 have developed a carbonylative approach to the synthesis of diversely substituted 2-aroylbenzoate esters featuring a new protocol for the carbonylative coupling of aryl bromides with boronic acids and a new strategy to favour carbonylative over non-carbonylative reactions. Two different synthetic pathways – (i) the alkoxycarbonylation of 2-bromo benzophenones and (ii) the carbonylative Suzuki–Miyaura ...

In 1987, the late German chemist Peter Hofmann of the University of Heidelberg wrote: “We still have a long way to go until a computation will be able to compete with or to substitute a lab experiment... one could then conclude that theoretical work in this field—not being quantitatively reliable anyhow—is rather useless, except for the purpose of keeping theorists busy.” However, Hofmann continued: ...

A series of metal–metal bonded osmium corrole dimers, {Os[TpXPC]}2, were synthesized in reasonably good yields (35–46%) via the interaction of the corresponding free-base meso-tris(p-X-phenyl)corroles (H3[TpXPC], X = CF3, H, CH3, and OCH3), Os3(CO)12, and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of ...

In transition metal-mediated carboxylation reactions, CO₂ inserts into a metal–nucleophile bond. At the carboxylation transition state (TS), CO₂ may interact with the metal (<i>inner</i>-sphere path) or may insert without being activated by the metal (<i>outer</i>-sphere path). Currently, there is no consensus as to which path prevails. In order to establish general predictions ...

The question of ligand noninnocence in Cu corroles has long been a topic of discussion. Presented herein is a Cu K-edge X-ray absorption spectroscopy (XAS) study, which provides a direct probe of the metal oxidation state, of three Cu corroles, Cu[TPC], Cu[Br8TPC], and Cu[(CF3)8TPC] (TPC = meso-triphenylcorrole), and the analogous Cu(II) porphyrins, Cu[TPP], Cu[Br8TPP], and Cu[(CF3)8TPP] (TPP = ...