Herein, we report a visible light-induced synthesis of sulfenamides via the oxidative coupling of amines with thiols using O as an oxidant. The photoreaction was conducted under simple and mild conditions, without any photocatalysts, metals, or additives. Detailed mechanistic studies revealed that a sulfur radical is generated through a single-electron transfer from an in situ-generated sulfur anion to O under visible light irradiation. This radical intermediate couples to form disulfide, which subsequently undergoes aminolysis to produce sulfenamides.

An efficient and expeditious method to assemble -bridged polycycles bearing up to six contiguous stereocenters from a gold(I)-catalyzed [3 + 2] cycloaddition/unactivated C(sp)-H bond insertion cascade of -1,6-enynyl benzaldehydes at a low catalyst loading of 2 mol % is described.

Aryl migration, especially 1,4-aryl migration, is one of the most important reactions in radical rearrangement. Over the past decades, 1,4-aryl migration by the addition of a radical to alkynes has become a simple and efficient method in the difunctionalization reactions of alkynes. Radical-based 1,4-aryl migration of aryl alkynoates has been well-explored; however, the 1,4-aryl migration of aryl propynyl ethers is rarely studied. Herein, we first described radical 1,4-aryl migration of propargyl ether to valuable α,β-unsaturated aldehydes via photoredox and Ni catalysis. This method features redox-neutral conditions, readily available starting materials, broad substrate scope, good functional group compatibility, and diverse transformations. Mechanistic studies suggest that this reaction proceeds through a radical-involved pathway.

Two planar BN doped benzofluorenes ( and ) were synthesized separately through palladium-catalyzed intramolecular C-C or C-N coupling reactions. The structures of both and are unambiguously confirmed by X-ray crystallographic analysis. Moreover, the BN unit doping leads to a much lower HOMO level and higher LUMO level as compared to their carbon analogues and . In comparison to and , both and exhibit blue shifts in their ultraviolet-visible (UV-vis) absorption and fluorescence emission spectra. Furthermore, halogenation of and afforded monohalogenated BN-benzofluorenes in good yields. These monohalogenated BN-benzofluorenes can serve as convenient intermediates for palladium-catalyzed coupling reactions to yield a series of functionalized BN-benzofluorene derivatives. The UV-vis absorption and emission spectroscopies in dichloromethane of these BN-benzofluorene derivatives were studied, and the photophysics of these compounds exhibited a high degree of substituent dependency.

A simple visible-light-promoted iron-catalyzed aerobic oxidative C-C bond cleavage of vicinal diols was developed. This reaction avoids the use of noble metal catalysts or specialized oxidants, yielding aldehydes and ketones without overoxidation. The new method works under air and at room temperature and features mild conditions and simple operation. Notably, the protocol is applicable for complex natural products, achieving the bioinspired conversion of the natural abundant diterpene oridonin to the natural rare enmein-type diterpene.

The stereoselective synthesis of (/)-α-aryl α,β-unsaturated carbonyl compounds remains a significant synthetic challenge. Recently, we demonstrated a novel -selective α-arylation of α,β-unsaturated nitriles via a Morita-Baylis-Hillman-type sulfonium [3,3]-rearrangement. In this study, we report that switching the base from KCO to 4-methoxypyridine in the final elimination step reverses the stereochemistry of the products from - to -geometry. Consequently, /-divergent α-arylation of α,β-unsaturated nitriles was achieved through these sulfonium rearrangements. Additionally, mechanistic studies reveal that weak interactions such as hydrogen bonding, n-π or π-π interactions, and short-range steric repulsions play crucial roles in determining the stereochemistry of the reaction.

Synthetic methods that feature mild reaction conditions and broad functional group tolerance are highly desired for the development of third-generation boron delivery agents, which are highly significant for boron neutron capture therapy (BNCT), a selective cancer treatment technique. Molecules containing carborane are promising candidates as boron delivery compounds for BNCT. Herein, we report an efficient radical thiol-ene "click" reaction involving carboranyl thiols and unactivated alkenes under photoredox conditions. This reaction affords moderate to excellent isolated yields. The current methodology allows for the incorporation of carborane, a valuable moiety with a high boron content, into molecules under mild reaction conditions. The outstanding functional group tolerance of this method makes it suitable for the late-stage introduction of boron into bioactive molecules. The radical addition reactivity of carboranyl thiol radical was investigated by DFT calculations to uncover the impact of the 3D aromaticity of carborane on the stabilization of a sulfur centered radical.

We demonstrate that polysulfide anions are capable of catalyzing desulfonylation of sulfonamides having a series of aryl and alkyl substituents in the presence of potassium formate under irradiation with visible light. The developed protocol is operationally concise and cost-effective, representing a practical and sustainable synthetic tool for desulfonylation and expanding the chemical space in secondary amine synthesis.

Asymmetric synthesis of chiral -hydroxyethyl amino indane derivatives remains challenging. In this study, an imine reductase mutant (IR262-F185E/F229L) was identified with high enantioselectivity toward various -hydroxyethyl imino derivatives. Furthermore, a continuous fed-batch strategy was designed to avoid the hydrolysis of imines, and up to 200 mM 1-((2-hydroxyethyl)imino)-2,3-dihydro-1-indene-4-carbonitrile could be completely converted into ()-1-((2-hydroxyethyl)amino)-2,3-dihydro-1-indene-4-carbonitrile in 70% isolated yield and >99% ee, demonstrating a great potential for the synthesis of the ozanimod intermediate in industrial applications.

Herein we describe the first transition-metal-catalyzed asymmetric Cloke-Wilson rearrangement through unprecedented propargylic alkenoxylation reaction with enol as the -nucleophile. A set of new chiral PPBOX ligands was prepared to guarantee the high enantioselectivity of the transformation. A series of polysubstituted dihydrofuran skeletons bearing an alkyne unit was prepared in good yield and high enantioselectivity under very mild reaction conditions, and various downstream transformations were facilely conducted to access different chiral skeletons.

Owing to the toxic reagent and high temperature required, the application of xanthate-based radical chemistry has been limited. To address these challenges, we report a metal- and base-free, photoinduced strategy for stereoselective -alkyl glycosylation via electron donor-acceptor (EDA) complexes of glycosyl xanthates and N-heterocyclic carbene (NHC)-BH. This method generates glycosyl radicals under mild conditions, affording compatibility with a wide range of sugars and olefins to produce -alkyl glycosides in good to excellent yields. Mechanistic studies confirmed the formation of EDA complexes and the involvement of radical intermediates, providing insights into the reaction pathway.

Herein, we report a catalytic reductive [4+1] sila-cycloaddition between functionalized 1,3-dienes and chemical feedstock di-, tri-, and tetrachlorosilane(s), enabled by a cost-effective pyridine-diimine-nickel complex, providing a practical method to prepare diverse silacyclopent-3-enes in up to 92% yield, including bridged and spiro silacarbocycles. This reaction demonstrates a broad substrate compatibility, including 1,3-dienes with different substitution patterns and a more accessible / isomeric mixture. Notably, trichlorosilanes undergo tandem [4+1] sila-cycloadditions/nucleophilic substitutions, while tetrachlorosilane successfully performs double [4+1] sila-cycloadditions with 2 equiv of 1,3-dienes to directly construct spiro silacarbocycles.

This study describes a novel and general protocol featuring organophotoredox-catalyzed intramolecular decarboxylative construction of carbon-heteroatom (oxygen, nitrogen, and sulfur) bonds, enabling direct access to ampakine APIs (CX-614 and CX-554), quinazolinone alkaloids (deoxyvasicinone and mackinazolinone), and thiazinone scaffolds as well as their congeners with broad functional group tolerance and scalability. Mechanistic studies suggest a radical-polar crossover pathway via single-electron oxidation.

Alkyl azetidines have been prepared by photochemical modifications of azetidine-2-carboxylic acids and . The reaction has been realized in milligram, gram, and even multigram quantities. The obtained azetidines are valuable building blocks for drug discovery.

Allyl thioesters, thiocarbonates, thiocarbamates, and thiocyanates are shown to undergo rhodium-catalyzed addition of carbene groups, generated from diazo compounds, to afford -acyl sulfonium ylides that undergo [2,3] sigmatropic rearrangement. Competing side reactions such as cyclopropanation and [1,2] acyl shifts are not observed. The reaction works with a variety of sulfur functional groups, including thioesters, thiocarbonates, thiocarbamates, and thiocyanates, affording densely functionalized products. The reaction works well with trimethylsilyldiazomethane (TMSD) and α-aryl diazoesters.

Five new macrocyclic napyradiomycins with different types of scaffolds were isolated from marine-derived SJ-019. Compounds and are uniquely typified by a spirocyclic core, while , and also contain a unique macrolide structure not known in any other napyradiomycins. Compound is composed of a dearomatized napyradiomycin core and an intramolecular double-arch bridge system. Compound displays potent inhibition of , while C-type napyradiomycin shows notable anti-inflammatory effect.

Here, we report a general and practical Doyle-Kirmse reaction of allyl/propargyl sulfides with donor-only vinyl carbenes generated from vinyl triftosylhydrazones in the presence of a silver catalyst. This protocol features mild conditions, exhibits a broad substrate scope and exceptional functional group tolerance, and provides corresponding 1,5-dienyl and 1,4-enallenyl sulfides in high yields. Moreover, gram-scale synthesis, late-stage modifications of complex molecules, and post-synthetic transformations were performed to demonstrate the applicability of this protocol.

Modifying the core structure of porphyrin dyes significantly impacts their electronic properties. However, the structure-property relationships of azaacene-fused heteroporphyrins remain underexplored. This study presents the synthesis and electronic properties of novel azaacene-fused 21,23-dithiaporphyrins. These dyes exhibit markedly red-shifted optical properties, reaching the near-infrared (NIR) region upon protonation and emitting in the NIR region in the neutral state.

Herein, we report an Fe/Co dual-catalyzed strategy for synthesizing alkenyl unnatural amino acids and peptide modifications. This approach utilizes aspartic acid and glutamic acid derivatives as alkyl radical precursors. It avoids the use of expensive photoredox catalysts and substrate preactivation while preserving the chirality of the amino acids. Furthermore, this strategy enables both modification of peptides and the synthesis of amino-acid-based drug candidates for boron-neutron capture therapy (BNCT).

Here, we report the use of iminosulfur oxydifluorides, derived from SOF and primary amines, for the generation of the unprecedented aza-analogues of fluorosulfury azide (FSON), namely, fluorosulfonimidoyl azide (R-N═SOFN). Unlike FSON, R-N═SOFN acts as a sulfamoyl nitrene precursor, undergoing imidation with sulfoxides and thioethers to from products featuring unique "-N = S(VI)F-N = S(VI)-" linkages without metal catalyst. The fluoride at the S(VI) center can be sequentially exchanged to generate diverse three-deminsional structures with tunable SuFEx reactivity. Mechanistic studies reveal that R-N = SOFN decomposes to the sulfamoyl nitrene intermediate, which is stabilized by the adjacent "-S(VI)=N-" nitrogen atom. This facilitates the formation of three-membered rings that react further with S(IV)/S(II). These novel transformations expand the scope of SOF-based SuFEx chemistry, demonstrating that R-N = SOFN enables dual reactivity through both nitrene-driven and tunable SuFEx-based linkages.

The proton-coupled electron transfer (PCET) process has garnered significant attention in photocatalysis due to its ability to facilitate challenging transformations under mild conditions. By integrating PCET into heterogeneous photocatalysts, substrates can be precisely activated through the concurrent transfer of both electrons and protons between the catalyst and reaction medium. Herein, we synthesized a novel type of carbon-nitride-based photocatalyst, which can effectively drive the reaction via the PCET mechanism, enabling the three-component synthesis of unsymmetrical imidazolidines with ease.