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.

Partially acetylated carbohydrates are integral to several biological functions and serve as synthetic intermediates for accessing complex glycoconjugates and oligosaccharides; however, their chemical synthesis remains highly challenging. Herein, we describe a straightforward protocol for the synthesis of monoacetylated sugars through acid-catalyzed regioselective deacetylation of readily accessible peracetylated glycosides featuring a cleavable aglycone (4-methoxyphenyl). The protocol proved effective for β-1,2-trans and α-1,2-cis-configured peracetylated pyranosides and its utility was demonstrated by large-scale synthesis, optimization for continuous flow, and application towards oligosaccharide synthesis.

Non‐typical C‐functionalized sugars represent a prominent yet hardly accessible class of biologically‐active compounds. The available synthetic methodologies toward such sugar derivatives suffer either from an extensive use of protecting groups, requiring long and laborious synthetic manipulations, or from limited predictability and noncontrollable site‐selectivity of the employed C‐functionalization reactions. In this work, we disclose an alternative synthetic methodology toward nontypical sugars that allows facile, site‐selective, and stereocontrolled C‐functionalization of sugars through a traceless tethering approach. The described silyl‐based redox‐active tethering group appends directly to the unprotected sugar substrate and mediates the C‐functionalization reaction through a photochemically‐promoted 1,6‐hydrogen atom transfer (HAT) mechanism, while transforming into a readily‐removable silyl protecting group. The protocol is compatible with a variety of unprotected carbohydrate substrates featuring sensitive aglycons and a diverse set of coupling partners, providing a straightforward and scalable route to pharmaceutically relevant C‐functionalized carbohydrate conjugates.

A controlled silver-catalyzed cycloaddition reaction of α,β-unsaturated nitroketones with isocyanides has been developed, facilitating the construction of polysubstituted pyrroles. This protocol addresses the issue of side reactions associated with the high reactivity of the aldehyde group in conventional reactions by employing a synergistic strategy for the protection and deprotection of the aldehyde group. Additionally, the nitrone moiety stabilizes the cycloaddition transition state through spatial electronic effects and is spontaneously deprotected to yield aromatization products.

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.

Herein, we present a prominent metal-free C–N cross-coupling platform that enables access to carbamoyl- and ketoazides from isocyanides or silyl enol ethers and trimethylsilyl azide (TMSN3) with an aid of iodine(III) promoter. This offers a rapid route to a diverse set of synthetically valuable azide decorated fragments with excellent substrate scope and good to excellent yields. The disclosed platform exemplifies the use of TMSN3 for incorporation of the azide fragment without the loss of N2.

Unnatural α-amino acids constitute a fundamental class of biologically relevant compounds. However, despite the interest in these motifs, synthetic strategies have traditionally employed polar retrosynthetic disconnections. These methods typically entail the use of stoichiometric amounts of toxic and highly sensitive reagents, thereby limiting the substrate scope and practicality for scale up. In this work, an efficient protocol for the asymmetric synthesis of unnatural α-amino acids is realized through photoredox-mediated C-O bond activation in oxalate esters of aliphatic alcohols as radical precursors. The developed system uses a chiral glyoxylate-derived N-sulfinyl imine as the radical acceptor and allows facile access to a range of functionalized unnatural α-amino acids through an atom-economical redox-neutral process with CO₂ as the only stoichiometric byproduct.

Herein, we report a silver-catalyzed protocol for decarboxylative cross-coupling between carboxylic acids and isocyanides, leading to linear amide products through a free-radical mechanism. The disclosed approach provides a general entry to a variety of decorated amides, accommodating a diverse array of radical precursors, including aryl, heteroaryl, alkynyl, alkenyl, and alkyl carboxylic acids. Notably, the protocol proved to be efficient for decarboxylative late-stage functionalization of several elaborate pharmaceuticals, demonstrating its potential applications.

Herein, we report a mild and general protocol for chemoselective deacetylation of mixed acetyl- and benzoyl-protected carbohydrates under mild acidic conditions. The protocol allows quick access to partially protected carbohydrates, which serve as versatile synthetic intermediates during the total synthesis of various mono- and oligosaccharide targets. The applicability of the developed protocol was successfully demonstrated on a range of carbohydrate substrates of various configurations and substitution patterns featuring functionalized aliphatic and aromatic aglycones. The protocol has shown excellent compatibility with the widely used O-anomeric protecting groups, prespacer aglycones, and thioglycoside glycosyl donors.

A silver-catalyzed protocol for the intermolecular radical umpolung cross-coupling protocol of silyl enol ethers with activated methylene compounds is disclosed. The protocol exhibits excellent functional group tolerance, enabling the expedient preparation of a variety of tricarbonyl compounds. Preliminary mechanistic investigations suggest that the reaction proceeds through a process involving free radicals in which silver oxide has a dual role, acting as both a catalyst and a base.