ortho‐Selective Phenol‐Coupling Reaction by Anodic Treatment on Boron‐Doped Diamond Electrode Using Fluorinated Alcohols

Enlarged scope by fluorinated mediators : Oxyl radicals are easily formed on boron‐doped diamond (BDD) electrodes and can be exploited for the ortho‐selective coupling to the corresponding biphenols (see scheme). At partial conversion, a clean transformation is achieved that can be applied to electron‐rich as well as fluorinated phenols.

     

Aerobic and Electrochemical Oxidative Cross‐Dehydrogenative‐Coupling (CDC) Reaction in an Imidazolium‐Based Ionic Liquid

The ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate [BMIm][BF₄] has demonstrated high efficiency when applied as a solvent in the oxidative nitro‐Mannich carbon? carbon bond formation. The copper‐catalyzed cross‐dehydrogenative coupling (CDC) between N‐phenyltetrahydroisoquinoline and nitromethane in [BMIm][BF₄] occurred with high yield under the described reaction conditions. Both the ionic liquid and copper catalyst were recycled nine times with almost no lost of activity. The electrochemical behavior of the tertiary amine substrate and β‐nitroamine product was investigated employing [BMIm][BF₄] as electrolyte solvent. The potentiostatic electrolysis in ionic liquid afforded the desired product with a high yield. This result and the cyclic voltammetric investigation provide a better understanding of the reaction mechanism, which involves radical and iminium cation intermediates.     

Electrochemically Active Cross‐Linking Reaction for Fluorescent Labeling of Aliphatic Alkenes

Although cross‐linking reactions serve as a valuable tool for the integration of two or more functionalities or properties, the application of electrochemical synthesis to cross‐linking reactions is restricted due to the difficulty of mass transfer. Thus, the primary purpose of this research is to explore electrochemical cross‐linking systems to construct a fluorescent probe, triggered by the formation of a covalent linkage. The second purpose is to apply the probe to insoluble targets. Towards these goals, a combination of electrochemically active phenol derivatives and aliphatic alkenes were employed to form polycyclic compounds. Several of the dihydrobenzofuran derivatives formed through [3+2] cyclization reactions exhibited fluorescence. Furthermore, this approach allowed the effective modification of alkene‐modified silica gel with electrochemically active species, which enables the construction of fluorescent probes that are triggered by C? C bond formation.     

Structure–Reactivity Relationships in Negishi Cross‐Coupling Reactions

Competition experiments have been performed to determine the relative reactivities of substituted bromobenzenes and of different arylzinc reagents in the [Pd(PPh₃)₄]‐catalyzed Negishi cross‐coupling reaction in THF at 25 °C. The cross‐coupling reactions are accelerated by electron acceptors in the bromobenzenes, the effect of which increases in the order ortho <meta <para. On the other hand, electron acceptors in the arylzinc halides diminish the reaction rates. Hammett correlations show that substituent variations in the bromobenzenes (ρ=+2.5) have a larger effect than substituent variations in the arylzinc halides (ρ=?0.98).     

Palladium‐Catalysed Cross‐Coupling of Vinyldisiloxanes with Benzylic and Allylic Halides and Sulfonates

The Hiyama cross‐coupling reaction is a powerful method for carbon–carbon bond formation. To date, the substrate scope of this reaction has predominantly been limited to sp²–sp² coupling reactions. Herein, the palladium‐catalysed Hiyama type cross‐coupling of vinyldisiloxanes with benzylic and allylic bromides, chlorides, tosylates and mesylates is reported. A wide variety of functional groups were tolerated, and the synthetic utility of the methodology was exemplified through the efficient total synthesis of the cytotoxic natural product bussealin A. In addition, the antiproliferative ability of bussealin A was evaluated in two cancer‐cell lines.     

Cross‐Coupling Reactions of Organosilicon Compounds in the Stereocontrolled Synthesis of Retinoids

This paper presents a full account of the use of Hiyama cross‐coupling reactions in a highly convergent approach to retinoids in which the key step is construction of the central C10? C11 bond. Representatives of two families of oxygen‐activated dienyl silanes (ethoxysilanes and silanols) and of all reported families of “safety‐catch” silanols (siletanes, silyl hydrides, allyl‐, benzyl‐, aryl‐, 2‐pyridyl‐ and 2‐thienylsilanes) were regio‐ and stereoselectively prepared and stereospecifically coupled to an appropriate electrophile by treatment with a palladium catalyst and a nucleophilic activator. Both all‐trans and 11‐cis‐retinoids, and their chain‐demethylated analogues, were obtained in good yields regardless of the geometry (E/Z) and of the steric congestion in each fragment. This comprehensive study conclusively establishes the Hiyama cross‐coupling reaction, with its mild reaction conditions and stable, easily prepared, ecologically advantageous silicon‐based coupling partners, as the most effective route to retinoids reported to date.     

Post‐Modification of meso–meso‐Linked Porphyrin Arrays by Iridium and Rhodium Catalyses for Tuning of Energy Gap

Skillfully attached! meso–meso‐Linked diporphyrins can be efficiently and selectively functionalized with multiple unsaturated carboxylic acid groups through iridium and rhodium catalyses. This post‐modification strategy allows fine‐tuning of energy levels of each porphyrin unit.

     

Functional‐Group‐Tolerant Catalytic Migratory Oxidative Coupling of Nitrones

A copper‐catalyzed migratory oxidative‐coupling reaction between nitrones and various ethers/amines exhibited high functional‐group tolerance. Even in aqueous media, the reaction proceeded efficiently. For practical use of this catalysis, a unique sequential Huisgen cycloaddition was demonstrated. Mechanistic investigations revealed that the reaction proceeded through oxidative catalytic activation of ethers/amines to afford iminium/oxonium intermediates by concurrent dual one‐electron abstractions by copper(II) and oxyl radicals.