Themed collection Most popular 2023 organic chemistry articles

By drawing inspiration from photoredox catalysis, the field of radical-mediated alkane functionalization has made remarkable advancements recently to address the challenges of today and future.

Dearomative cycloaddition is a powerful technique to access sp³-rich three-dimensional structural motifs from simple flat, aromatic feedstock.

This review explores the benefits of flow chemistry and dispels the notion that it is a mysterious “black box”, demonstrating how it can push the boundaries of organic synthesis through the understanding of its governing principles.

We report the discovery of an ortho regioselective oxidative halodeboronation of N-aryl amides and ureas with wide-ranging applications in pharmaceuticals, materials science, and synthetic organic chemistry.

Benzoyldiisopropylchlorosilane (BDIPSCl), an acylchlorosilane that represents a new class of acylsilanes, is introduced as a new visible light photocleavable silicon-based alcohol protecting group.

This work unlocks the use of anilines in the selective trifluoromethylarylation of olefins via a mild protocol that avoids transition metals, expensive photocatalysts and additives, where hexafluoroisopropanol is a unique solvent that promotes it.

An intriguing chiral phosphoric acid-catalyzed asymmetric hydrolytic ring-opening of racemic aziridines via regiodivergent PKR is presented, providing an efficient approach for the construction of chiral β-amino alcohols.

Site-selective and direct C–F bond functionalization of polyfluorinated iminosulfides was achieved to synthesize 3-fluoro-3-perfluoroalkyl-γ-lactams under photoredox-neutral conditions.

We have developed a divergent approach for the catalytic asymmetric synthesis of skeletally different benzofuran fused azocine derivatives and spiro-cyclopentanone benzofurans. The methodology involves sequential catalysis: chiral H-bonding catalysis and Lewis base catalysis.

Carboxylic acids can be converted directly to bioisosteric 3-oxetanols by leveraging the unique reactivity of photoredox catalysis. Cr-mediated and Cr-free variants of the reaction have been developed, both having quantum yields greater than 5.

An azido-alkynylation of alkenes has been developed by combining hypervalent iodine reagents and alkynyl-trifluoroborate salts. This method allows the synthesis of homopropargylic azides, which could be transformed into pyrroles or bioactive amines.

Two types of chiral gem-difluoroalkyl reagents, chiral gem-difluoroalkyl propargylic borons and gem-difluoroalkyl α-allenols were developed by means of Rh-catalyzed enantioselective B–H bond insertion and Lewis acid-promoted allenylation.

We demonstrate a simple strategy to use a metal surface to directly catalyse mechanochemical reactions by Resonant Acoustic Mixing (RAM), a scalable mechanochemical methodology that uniquely eliminates the need for grinding media or bulk solvent.

A cobalt-catalyzed atroposelective C–H/N–H annulation of sulfonamides with allenes or alkynes, using either chemical or electrochemical oxidation, was disclosed, which affords C–N axially chiral sultams with high regio- and enantio-selectivities.

A sequential C–H gem-difunctionalization of 1,3-benzodioxoles with α-trifluoromethyl alkenes and electron-deficient alkenes in a redox-neutral radical polar crossover manifold have been developed for the synthesis of monofluorocyclohexenes.

EDA complexes with catalytic triarylamines allow C–H perfluoroalkylation of arenes and heteroarenes under visible light irradiation in pH- and redox-neutral conditions. A detailed photophysical characterization of the EDA complex is provided.

Technology for generating especially important amide and peptide bonds from carboxylic acids and amines that avoids traditional coupling reagents is described.

We report a convenient protocol for a nitrogen atom insertion into indenes to afford isoquinolines. The strategy further enables the synthesis of pyridines from cyclopentadienes and a facile access to ¹⁵N labelled isoquinolines.

1-Azahomocubane has been prepared 56 years after the parent hydrocarbon. Introduction of a nitrogen atom into this constrained polycyclic environment resulted in minimal changes to the framework geometry, with s-character of the nitrogen lone pair increasing due to strain.

The development of strategies for single and selective C–F bond activation represents an important avenue to overcome limitations in the synthesis of valuable fluorine-containing compounds.

Near-infrared absorbing oxocarbon derivatives, so-called squaraine and croconaine dyes, regarded as closed-shell species so far, display the intermediate open-shell character that impacts their one- and two-photon absorption properties.

A metal-free deaminative coupling of non-prefunctionalised benzylamines and arylboronic acids is reported.

A novel photoinduced heteroarylation route to substituted oxindoles is disclosed.

It has been a long-standing challenge to achieve catalytic asymmetric X–H bond insertion with free carbenes. Herein, an indirect visible-light-promoted asymmetric N–H insertion is disclosed.

Constructing alkenyl sulfides has never been so easy! A new halogen-bonding assisted photochemical transformation allows for the catalyst free cross-coupling between vinyl halides and thiols under basic conditions and visible light irradiation.

Proof of concept enantioselective transformation via photoelectrocatalysis was reported on Cu-catalyzed enantioselective decarboxylative cyanation, which features mild conditions, high enantioselectivity and a reasonable range of functionalities.

A ball-milling approach allows the efficient activation of unactivated manganese metal and thus makes the direct generation of arylmanganese nucleophiles feasible without the need for complicated pre-activation processes and metal additives.

By merging paired electrolysis and cobalt catalysis, we have developed an electrochemical redox-neutral coupling for the synthesis of N-heteroaryl trifluoromethyl carbinols from readily available N-heteroarenes and trifluoromethyl ketones.