Divergent Synthesis and Crystal Engineering of Room-Temperature Phosphorescent Carbonyl-Bridged Triphenylamines.

Organic materials with room temperature phosphorescence (RTP) are a growing research topic, with recent investigations revealing a strong effect of the crystal packing on the RTP properties. However, these relationships are difficult to decipher, as the crystal packing affects both the intermolecular interactions and the molecular conformation. Here, we report a divergent synthetic strategy to generate a family of rigid carbonyl-bridged triphenylamine (TPA)-based chromophores via metal-free transformations of the same starting material, and exploit this family to investigate the effects of crystal packing on the solid state RTP properties.

A General Platform for Visible Light Sulfonylation Reactions Enabled by Catalytic Triarylamine EDA Complexes.

Catalytic electron donor-acceptor (EDA) complexes have recently emerged as a powerful and sustainable alternative to iridium- and ruthenium-based photoredox synthetic methods. Yet, these complexes remain underexplored and reliant on the use of meticulously designed acceptors that require previous installation. Herein, we report a novel EDA complex employing tris(4-methoxyphenyl) amine as a catalytic donor for the sulfonylation of alkenes using inexpensive and readily available sulfonyl chlorides.

Triarylamines as catalytic donors in light-mediated electron donor-acceptor complexes.

Recently, photochemistry of Electron Donor-Acceptor (EDA) complexes employing catalytic amounts of electron donors have become of interest as a new methodology in the catalysis field, allowing for decoupling of the electron transfer (ET) from the bond-forming event. However, examples of practical EDA systems in the catalytic regime remain scarce, and their mechanism is not yet well-understood. Herein, we report the discovery of an EDA complex between triarylamines and α-perfluorosulfonylpropiophenone reagents, catalyzing C-H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions.

EDA mediated S-N bond coupling of nitroarenes and sodium sulfinate salts.

Despite their long-known photochemical properties and their industrial value, the use of nitroarenes as a productive photochemical handle in organic synthesis has remained relatively unexplored. More specifically, the photochemical formation of nitrogen-sulfur bonds from nitroarenes remains to be demonstrated. Herein, we report the design and application of a sulfinate-nitroarene electron donor-acceptor (EDA) complex and its subsequent use in the first light mediated catalyst-free synthesis of hydroxy-sulfonamides.

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics.

In response to the demand for late-stage perfluoroalkylation in synthetic chemistry, we report the synthesis of a series of bench-stable α-(perfluoroalkylsulfonyl)propiophenones. Their application as photocleavable reagents was tested with electron-rich aromatics under metal-free, redox- and pH-neutral conditions to enable late-stage perfluorooctylation, perfluorohexylation, and perfluorobutylation.

Green chemistry meets medicinal chemistry: a perspective on modern metal-free late-stage functionalization reactions.

The progress of drug discovery and development is paced by milestones reached in organic synthesis. In the last decade, the advent of late-stage functionalization (LSF) reactions has represented a valuable breakthrough. Recent literature has defined these reactions as the chemoselective modification of complex molecules by means of C-H functionalization or the manipulation of endogenous functional groups.

Modern methods for the synthesis of perfluoroalkylated aromatics.

Perfluoroalkyl-containing substances (PFAS), have become omnipresent materials in the modern world for both commercial and research applications. Compounds such as perfluoroalkylated arenes and heteroarenes have found uses in surfactants, lubricants, and flame retardants as a result of their astonishing chemical stability. Consequently, the synthesis of such compounds encompasses a large body of scientific articles and patents developed in the previous century.

Synthesis of 2,5-Diaryl Nonsymmetric Furans C6-Platform Chemicals Catalytic Conversion of Biomass and the Formal Synthesis of Dantrolene.

Biomass-derived commodity chemical 5-hydroxymethyl furfural is an underutilized C6-platform chemical derived from cellulose that is ideal to prepare next-generation value-added products. We have developed an efficient synthetic strategy to access 2,5-diaryl nonsymmetric furans from 5-hydroxymethyl furfural utilizing decarboxylative cross-couplings. A key finding was that the presence of the hydroxymethyl handle enhances the yields of the palladium-catalyzed decarboxylative cross-coupling reaction.