A Non-Heme Iron(III) Complex with Porphyrin-like Properties That Catalyzes Asymmetric Epoxidation

In this report, we describe an iron­(III) complex containing a carbazole-based tridentate ligand that catalyzes highly enantioselective asymmetric epoxidation of (<i>E</i>)-alkenes at room temperature. The non-heme iron­(III) complex has a five-coordinated trigonal-bipyramidal structure, and its two-electron oxidized state has the similar electronic structure as that of iron porphyrins

A Non-Heme Iron(III) Complex with Porphyrin-like Properties That Catalyzes Asymmetric Epoxidation

In this report, we describe an iron­(III) complex containing a carbazole-based tridentate ligand that catalyzes highly enantioselective asymmetric epoxidation of (E)-alkenes at room temperature. The non-heme iron­(III) complex has a five-coordinated trigonal-bipyramidal structure, and its two-electron oxidized state has the similar electronic structure as that of iron porphyrins

Palladium-Catalyzed Direct Arylation of Aryl(azaaryl)methanes with Aryl Halides Providing Triarylmethanes

Direct arylation of aryl(azaaryl)methanes with aryl halides takes place at the benzylic position in the presence of a hydroxide base under palladium catalysis to yield triarylmethanes

Rhodium-Catalyzed <i>ipso</i>-Borylation of Alkylthioarenes via C–S Bond Cleavage

Rhodium-catalyzed transformation of alkyl aryl sulfides into arylboronic acid pinacol esters via C–S bond cleavage is reported. In combination with transition-metal-catalyzed sulfanyl group-guided regioselective C–H borylation reactions of alkylthioarenes, this method allows the synthesis of a diverse range of multisubstituted arenes

Stereoinversion of Stereocongested Carbocyclic Alcohols via Triflylation and Subsequent Treatment with Aqueous <i>N</i>,<i>N</i>‑Dimethylformamide

A convenient method for the stereoinversion of secondary alcohols, applicable to stereocongested carbocyclic substrates, is reported. A simple three-step procedure, including triflylation of the hydroxy group, nucleophilic oxygenative displacement by the treatment with aqueous <i>N</i>,<i>N</i>-dimethyl­formamide (DMF), and methanolysis, allowed for efficient stereoinversion of various substrates, including sugar derivatives, in one pot

Palladium-Catalyzed Benzylic Arylation of <i>N</i>-Benzylxanthone Imine

The direct benzylic arylation of N-benzylxanthone imine with aryl chloride proceeds under palladium catalysis, yielding the corresponding coupling product. The product is readily transformed to benzhydrylamine. Taking into consideration that the imine is readily available from benzylic amine, the overall transformation represents a formal cross-coupling reaction of aryl halide with α-aminobenzyl metal

Ni/Cu-Catalyzed Defluoroborylation of Fluoroarenes for Diverse C–F Bond Functionalizations

Ni/Cu-catalyzed transformation of fluoroarenes to arylboronic acid pinacol esters via C–F bond cleavage has been achieved. Further versatile derivatization of an arylboronic ester has allowed for the facile two-step conversion of a fluoroarene to diverse functionalized arenes, demonstrating the synthetic utility of the method

Palladium-Catalyzed <i>ipso</i>-Borylation of Aryl Halides Promoted by Lewis Acid-Mediated Electrophilic Activation of Aryl(halo)palladium(II) Complex

Palladium-catalyzed ipso-borylation of aryl halides, well-known as Miyaura borylation, is one of the reliable synthetic methods for organoborons. This reaction involves base-mediated nucleophilic activation of diboron that enables transmetalation of an aryl(halo)palladium(II) intermediate with a diboron. As an alternative, herein, we have established Lewis acid-mediated conditions for borylating (pseudo)haloarenes that require no external base. The electrophilic activation of the aryl(halo)palladium(II) intermediate via dehalogenation with Lewis acidic zinc complexes promotes the borylation

Preparation of Imides via the Palladium-Catalyzed Coupling Reaction of Organoborons with Methyl <i>N</i>‑[Methoxy(methylthio)methylene]carbamate as a One-Carbon Elongation Reaction

The preparation of imides via the palladium-catalyzed coupling reaction as a one-carbon elongation reaction is described. The palladium-catalyzed coupling reaction of aryl-, alkyl-, and alkenylborons with N-[methoxy(methylthio)methylene]carbamate in the presence of Cu(I) thiophene-2-carboxylate (CuTC) affords imino ethers that are converted to the corresponding imides by acidic hydrolysis in high yield. The imino ethers are also useful for preparing the corresponding ester without using carbon monoxide