Abstract Carbenes are very important reactive intermediates to access a variety of complex molecules and applied widely in organic synthesis drug discovery. Typically, their chemistry is accessed by the use transition metal catalysts. Herein, we describe application low‐energy blue light for photochemical generation carbenes from donor–acceptor diazoalkanes. This catalyst‐free operationally simple approach enables highly efficient cyclopropenation reactions with alkynes rearrangement...

Novel iodine-induced sulfonylation and sulfenylation of imidazopyridines have been described using sodium sulfinates as the sulfur source. This strategy enables highly selective difunctionalization imidazo[1,2-a]pyridine to access sulfones sulfides in good yields. A wide range substrates functional groups were well-tolerated under optimized conditions. Moreover, control experiments conducted, indicating a radical pathway involved reaction mechanisms.

Cyclopropanation reactions of carbenes with arenes provide a straightforward pathway to norcaradienes or cycloheptatrienes. This reaction normally requires harsh conditions transition-metal catalysts. In this report, we describe the metal-free visible-light photolysis aryl diazoacetates in aromatic solvents, which provides access norcaradiene ring system highly regio- and stereoselective manner. The mild approach also allow chemoselective cyclopropanation substituted without competing C-H...

Abstract Sigmatropic rearrangement reactions constitute one of the most fundamental carbenes. While state‐of‐the‐art synthetic methods require use expensive precious metal catalysts, application visible light for photolysis α‐aryldiazoacetates is much less investigated and provides an operationally simple entry to carbenes under mild reaction conditions. Herein, we report on blue‐light induced sigmatropic sulfur compounds with α‐aryldiazoacetates. This process, depending substitution pattern...

Nitrene transfer reactions represent one of the key to rapidly construct new carbon-nitrogen bonds and typically require transition metal catalysts control reactivity pivotal nitrene intermediate. Herein, we report on application iminoiodinanes in amination under visible light photochemical conditions. While a triplet can be accessed catalyst-free conditions, use suitable photosensitizer allows access radical anion. Computational mechanistic studies rationalize anion allow direct comparison...

Significantly increasing the photothermal conversion of plasmonic nanostructured particles (PNPs) is a common goal for all applications thermoplasmonics, but it still in challenge, especially PNPs with morphology and composition required specific application. Here, we present concept defect-induced damping-enhanced conversion, which favors PNP intrinsic properties. A model defect-damped harmonic oscillator established to depict correlation structure capable accurately reproducing optical...

Trifluoromethylated aziridines are the smallest fluorinated N-heterocycle and represent important strategic building blocks with broad application in drug discovery for synthesis of functionalized, amines via ring-opening reactions. Their catalytic represents even today a major challenge organic chemistry, methods relying on classic nitrene transfer reactions electron-poor, olefins significantly hampered. Herein, we demonstrate that iodinanes undergo oxidative quenching presence simple...

A novel iron-involved tosylmethylation of imidazo[1,2-α]pyridines with p-toluenesulfonylmethyl isocyanide in a solvent mixture H2O and PEG400 under an Ar atmosphere has been developed. This protocol provides facile synthetic route for the functionalization imidazo[1,2-α]pyridine scaffold broad substrate compatibility, which is less expensive environmentally friendly. The current methodology could further enable regioselective C-H indole at C3 position. Also, was utilized as tosylmethylating...

Benzyl thioethers undergo rhodium(ii) catalyzed sigmatropic rearrangement reactions with aryldiazoacetates. Depending on the solvent and electronic properties of sulfide, intermediate ylide undergoes either [1,2]- or [2,3]-sigmatropic in high yields.

This study reports a photocatalytic nitrene transfer reaction of 1,3-dicarbonyl. A broad range substrates and iodinanes are shown, enabling direct C–H functionalization without the need for pre-formed nucleophilic enolate equivalents.

Abstract Carbene sind wichtige reaktive Intermediate, die den Zugang zu einer Vielzahl von komplexen Molekülen ermöglichen und eine große Anwendung in der organischen Chemie Wirkstoffforschung besitzen. In Regel wird diese durch Verwendung Übergangsmetallkatalysatoren ermöglicht. Im Folgenden beschreiben wir niederenergetischem Licht zur photochemischen Erzeugung Carbenen ausgehend Donor‐Akzeptor‐Diazoalkanen. Dieser katalysatorfreie präparativ einfache Ansatz ermöglicht hoch effiziente...

We report on the use of visible light to conduct carbene-transfer reactions donor/acceptor diazoalkanes with cyclooctatetraene and polyunsaturated carbocycles give corresponding cyclopropanes in excellent yields stereoselectivities. This photochemical protocol proved be superior conventional metal-catalyzed cyclopropanation now provides platform chemicals containing a cyclic conjugated all-cis triene. The cyclopropane is an important structural feature prevent 6π electrocyclization. Instead,...

Abstract Photochemical, metal‐free nitrene transfer reactions for C−H amination, aziridination, or sulfilimination are highly desirable. Yet, photochemical of nitrenes with sulfides underdeveloped as singlet species would be required a productive reaction. Herein, we describe the blue‐light‐mediated reaction using iminoiodinanes. We developed protocol efficient stoichiometric reaction, which allows synthesis sulfilimines in only 10 minutes time. further applied our procedure towards allyl...

Nitrene, as an important and intriguing versatile synthon, is widely utilized for the formation of diverse nitrogenous skeletons under thermal or photochemical conditions. Typically, N-sulfonyl nitrenes could be smoothly generated from iminoiodinanes at relatively low reaction temperatures to generate nitrenes. Herein, we described direct immidation with sulfoxides through a blue-light-induced transfer process. This strategy offers efficient gentle pathway directly obtaining sulfoximines...

We report on a photochemical reaction of silyl enol ethers with iminoiodinanes.

Abstract This work proposes a novel and simple synthesis method for microporous‐ceria‐wrapped gold (Au@mp‐CeO 2 ) nanoparticles (NPs) based on linker molecule‐induced stacking of ultrafine CeO particles (or beads) the surface pre‐prepared NPs. The resulting NPs have uniform size microporous shells with mean thickness 28 nm porosity 42%. shell is highly tunable from about 4 to 30 thick. universal suitable other metal@mp‐oxide nanoarchitectures (such as Au@mp‐CuO NPs, Au@mp‐Cr O 3 Ag@mp‐CeO...

Spherical Janus micromotors (SJMs) have attracted much attention, and their high-speed motion is highly desired due to various potential applications. However, the conventional template-deposition method often leads an active Pt coating with a smooth surface, which unbeneficial speed enhancement in terms of catalytic reaction. Here, facile surface roughening presented fabricate Pt-polystyrene (PS) SJMs rough (or Ptr-PS SJMs) by plasma-etching PS colloidal monolayer then depositing Pt. The...

Abstract Cyclopropanation reactions of d ‐glucal and ‐galactal derivatives with aryldiazoacetates can be conducted in a substrate‐controlled, stereoselective fashion using simple Rh(II) catalysts, which is further supported by DFT studies. Following this methodology, sugar‐derived, donor‐acceptor cyclopropanes accessed that allow O ‐glycosylation reactions.

The control of colloidal motors' motion is crucial for their practical applications. modulation the active component distribution on motors one effective routes to controlling but still in challenge. Here, Pt-TiO2 bilayered hemispherical nanoshells (BHNSs) with different Pt distributions are designed and fabricated via etching an organic template depositing TiO2 angles sequences. obtained include BHNSs complete outer inner layers (or TiO2/Pt Pt/TiO2 BHNSs) partially (P-BHNSs) incomplete...

Download This Paper Open PDF in Browser Add to My Library Share: Permalink Using these links will ensure access this page indefinitely Copy URL Photochemical Nitrene Transfer Reactions of Iminoiodinanes with Sulfoxides KeAi: Green Synthesis & Catalysis 5 Pages Posted: 23 Feb 2024 Publication Status: Under Review See all articles by Xue-Mei ZhaoXue-Mei ZhaoZhengzhou UniversityZhiyuan TangZhengzhou UniversityLinlin ShiZhengzhou UniversityYujing GuoZhengzhou UniversityRene M. KoenigsRWTH Aachen...