Aminoalcohols are vital motifs in chemical synthesis; however, traditional synthetic technologies relying on polar disconnections have various limitations. Now, such motifs can be expediently accessed by leveraging a radical-based approach, enabling the stereoselective preparation of an array of valuable building blocks.

Aromatic compounds serve as key feedstocks in the chemical industry, typically undergoing functionalization or full reduction. However, partial reduction via dearomative sequences remains underexplored despite its potential to rapidly generate complex three-dimensional scaffolds and the existing dearomative strategies often require metal-mediated multistep processes or suffer from limited applicability. Herein, a photocatalytic radical cascade approach enabling dearomative difunctionalization through selective spirocyclization/imination of nonactivated arenes is reported. The method employs bifunctional oxime esters and carbonates to introduce multiple functional groups in a single step, forming spirocyclic motifs and iminyl functionalities via N–O bond cleavage, hydrogen-atom transfer, radical addition, spirocyclization, and radical-radical cross-coupling. The reaction constructs up to four bonds (C−O, C−C, C−N) from simple starting materials. Its broad applicability is demonstrated on various substrates, including pharmaceuticals, and it is compatible with scale-up under flow conditions, offering a streamlined approach to synthesizing highly decorated three-dimensional frameworks.

The instability of molecular electrodes under oxidative/reductive conditions and insufficient understanding of the metal oxide-based systems have slowed down the progress of H2-based fuels. Efficient regeneration of the electrode's performance after prolonged use is another bottleneck of this research. This work represents the first example of a bifunctional and electrochemically regenerable molecular electrode which can be used for the unperturbed production of H2 from water. Pyridyl linkers with flexible arms (-CH2-CH2-) on modified fluorine-doped carbon cloth (FCC) were used to anchor a highly active ruthenium electrocatalyst [RuII(mcbp)(H2O)2] (1) [mcbp2− = 2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine]. The pyridine unit of the linker replaces one of the water molecules of 1, which resulted in RuPFCC (ruthenium electrocatalyst anchored on -CH2-CH2-pyridine modified FCC), a high-performing electrode for oxygen evolution reaction [OER, overpotential of ∼215 mV] as well as hydrogen evolution reaction (HER, overpotential of ∼330 mV) at pH 7. A current density of ∼8 mA cm−2 at 2.06 V (vs. RHE) and ∼−6 mA cm−2 at −0.84 V (vs. RHE) with only 0.04 wt% loading of ruthenium was obtained. OER turnover of >7.4 × 103 at 1.81 V in 48 h and HER turnover of >3.6 × 103 at −0.79 V in 3 h were calculated. The activity of the OER anode after 48 h use could be electrochemically regenerated to ∼98% of its original activity while it serves as a HE cathode (evolving hydrogen) for 8 h. This electrode design can also be used for developing ultra-stable molecular electrodes with exciting electrochemical regeneration features, for other proton-dependent electrochemical processes.

Herein, a straightforward synthetic approach for the construction of phenanthridin-6(5H)-one skeletons is disclosed. The developed protocol relies on palladium catalysis, providing controlled access to a range of functionalized phenanthridin-6(5H)-ones in 59-88% yields. Furthermore, plausible reaction pathways are proposed based on mechanistic experiments.

Alcohols and their derivatives are ubiquitous and versatile motifs in organic synthesis. Deoxygenative transformations of these compounds are often challenging due to the thermodynamic penalty associated with the cleavage of the C−O bond. However, electrochemically driven redox events have been shown to facilitate the C−O bond cleavage in alcohols and their derivatives either through direct electron transfer or through the use of electron transfer mediators and electroactive catalysts. Herein, a comprehensive overview of preparative electrochemically mediated protocols for C−O bond activation and functionalization is detailed, including direct and indirect electrosynthetic methods, as well as photoelectrochemical strategies.

Establishing chemodivergent synthetic strategies remains a daunting task in the realm of free-radical reaction manifolds. In the December issue of Chem, Glorius and co-workers resolve this challenge for selective difunctionalization of aliphatic alkenes. In the disclosed light-promoted radical relay process, switchable trifluoromethylation/alkylation or trifluoromethylation/sulfonylation of alkenes is achieved.

The Wittig reaction is a valuable and powerful tool in organic synthesis, providing a convenient route from aldehydes and ketones to alkenes. Herein, a novel copper-assisted Wittig-type olefination of aldehydes with p-toluenesulfonylmethyl isocyanide (TosMIC) is disclosed, providing a direct and operationally simple approach to (E)-vinyl sulfones under mild conditions, compatible with a multitude of common functional groups. Experimental and computational investigations imply that the reaction proceeds through an intriguing electronically-controlled (3 + 2)/retro-(3 + 2) cycloaddition pathway.

Lignin, a major component of lignocellulose, constitutes the largest source for the production of aromatic building blocks, and offers considerable potential to serve as an entry to biobased products. During the past decades, substantial research activity has been noted in the pursuit of sustainable catalytic methods for accessing lignin-derived platform chemicals. However, the highly cross-linked and irregular structure has hindered the development of efficient and predictable deconstruction strategies from this renewable source. A majority of the developed methods for lignin depolymerization require harsh conditions including high-pressure atmospheres of gases, high temperatures, and prolonged reaction times. Considering the recent renewed interest in photocatalysis as a means for the mild and operationally simple generation of open-shell intermediates, it is not remarkable that such reaction manifolds have also been implemented towards lignin depolymerization. The tremendous potential of visible light photocatalysis for harnessing sustainable energy sources and reducing waste streams will certainly have an enduring impact in future green chemistry innovation.

Photoredox catalysis has recently emerged as a powerful synthetic platform for accessing complex chemical structures through non-traditional bond disconnection strategies that proceed through free-radical intermediates. Such synthetic strategies have been used for a range of organic transformations; however, in carbohydrate chemistry they have primarily been applied to the generation of oxocarbenium ion intermediates in the ubiquitous glycosylation reaction. In this Review, we present more intricate light-induced synthetic strategies to modify native carbohydrates through homolytic C–H and C–C bond cleavage. These strategies allow access to glycans and glycoconjugates with profoundly altered carbohydrate skeletons, which are challenging to obtain through conventional synthetic means. Carbohydrate derivatives with such structural motifs represent a broad class of natural products integral to numerous biochemical processes and can be found in active pharmaceutical substances. Here we present progress made in C–H and C–C bond activation of carbohydrates through photoredox catalysis, focusing on the operational mechanisms and the scope of the described methodologies. [Figure not available: see fulltext.]. 

Photo-mediated radical dearomatization involving 5-exo-trig cyclizations has proven to be an important route to accessing spirocyclic compounds, whereas 6-exo-trig spirocyclization has been much less explored. In this work, a dearomative annulation cascade is realized through photoredox-mediated C-O bond activation of aromatic carboxylic acids to produce two kinds of spirocyclic frameworks. Mechanistically, the acyl radical is formed through oxidation of triphenylphosphine and subsequent C-O bond cleavage, followed by a 6-exo-trig cyclization/SET/protonation sequence to generate the spiro-chromanone products in an intramolecular manner. Furthermore, the protocol was extended to more challenging intermolecular tandem sequences consisting of C-O bond cleavage, radical addition to an alkene substrate, and 5-exo-trig cyclization to yield complex spirocyclic lactams. Photo-mediated radical dearomatization involving 5-exo-trig cyclizations has proven to be an important route to accessing spirocyclic compounds, whereas 6-exo-trig spirocyclization has been much less explored. Here, a dearomative annulation cascade is realized through a photoredox-mediated C-O bond activation of aromatic carboxylic acids to produce two kinds of spirocyclic frameworks, whereby the spirocyclizations are triggered by acyl radical formation from benzoic acids leading to spiro-chromanones via a direct intramolecular 6-exo-trig cyclization or spirocyclic lactams via an intermolecular addition/5-exo-trig cyclization cascade.