Palladium-Catalyzed Carbonylative Esterification of Primary Alcohols with Aryl Chlorides through Dehydroxymethylative C–C Bond Cleavage

Aryl chlorides in the presence of Pd/C catalyst and NaF react with primary alcohols to form esters, arenes, and alkanes. In this reaction, aryl chlorides act as both oxidants and coupling partners, whereas alcohols serve as both carbonyl sources and alkoxy components of the ester product

Ir(I)/HCl Catalyzed Head-to-Tail Homocoupling Reactions of Vinylsilanes

Novel homocoupling reactions of vinylsilanes, catalyzed by a mixture of Ir(I) and HCl, were developed. This process leads to exclusive formation of head-to-tail vinylsilane dimers in high yields at room temperature. Synthetic attributes of transformations of the resulting head-to-tail vinylsilane dimers and polymerization of bis(vinylsilane) were investigated

Coupling Reagent for UV/vis Absorbing Azobenzene-Based Quantitative Analysis of the Extent of Functional Group Immobilization on Silica

A methallylsilane coupling reagent, containing both a <i>N</i>-hydroxy­succinimidyl­(NHS)-ester group and a UV/vis absorbing azobenzene linker undergoes acid-catalyzed immobilization on silica. Analysis of the UV/vis absorption band associated with the azobenzene group in the adduct enables facile quantitative determination of the extent of loading of the NHS groups. Reaction of NHS-groups on the silica surface with amine groups of GOx and rhodamine can be employed to generate enzyme or dye-immobilized silica for quantitative analysis

Synthesis of Pyrroles through Rhodium(III)-Catalyzed Reactions of Allylamines and Alkenes

Pyrrole derivatives are generated in reactions of allylamines with alkenes that are promoted by a Rh­(III) catalyst in the presence of AgOAc. This process, which involves chelation assisted C–H bond activation and <i>N</i>-annulation, is applied to a three step synthesis of Zomepirac

Hydroesterification of Alkenes with Sodium Formate and Alcohols Promoted by Cooperative Catalysis of Ru₃(CO)₁₂ and 2‑Pyridinemethanol

A chelation-assisted hydroesterification reaction of alkenes with sodium formate and alcohols that involves cooperative catalysis by Ru₃(CO)₁₂ and 2-pyridinemethanol is described. In this three-component coupling reaction, sodium formate serves as the carbon monoxide source

Ferric(III) Chloride Catalyzed Halogenation Reaction of Alcohols and Carboxylic Acids Using α,α-Dichlorodiphenylmethane

A new method for chlorination of alcohols and carboxylic acids, using α,α-dichlorodiphenylmethane as the chlorinating agent and FeCl₃ as the catalyst, was developed. The method enables conversions of various alcohols and carboxylic acids to their corresponding alkyl and acyl chlorides in high yields under mild conditions. Particulary interesting is the observation that the respective alkyl bromides and iodides can be generated from alcohols when either LiBr or LiI are present in the reaction mixtures

Directional Electron Transfer in Chromophore-Labeled Quantum-Sized Au₂₅ Clusters: Au₂₅ as an Electron Donor

Novel Au₂₅(C₆S)₁₇PyS clusters (pyrene-functionalized Au₂₅ clusters) showing interesting electrochemical and optical properties are synthesized and characterized. Significant fluorescence quenching is observed for pyrene attached to Au₂₅ clusters, suggesting strong excited-state interactions. Time-resolved fluorescence upconversion and transient absorption measurements are utilized to understand the excited-state dynamics and possible interfacial electron- and energy-transfer pathways. Electrochemical investigations suggest the possibility of electron transfer from Au₂₅ clusters to the attached pyrene. Fluorescence upconversion measurements have shown faster luminescence decay for the case of pyrene attached to Au₂₅ clusters pointing toward ultrafast photoinduced electron/energy-transfer pathways. Femtosecond transient absorption measurements have revealed the presence of the anion radical of pyrene in the excited-state absorption, suggesting the directional electron transfer from Au₂₅ clusters to pyrene. The rate of forward electron transfer from the Au₂₅ cluster to pyrene is ultrafast (∼580 fs), as observed with femtosecond fluorescence upconversion and transient absorption