Kei Murakami

Azines, which are six-membered aromatic compounds containing one or more nitrogen atoms, serve as ubiquitous structural cores of aromatic species with important applications in biological and materials sciences. Among a variety of synthetic approaches toward azines, C-H functionalization represents the most rapid and atom-economical transformation, and it is advantageous for the late-stage functionalization of azine-containing functional molecules. Since azines have several C-H bonds with differ

Since the discovery by Ullmann and Bielecki in 1901, reductive dimerization (or homocoupling) of aryl halides has been extensively exploited for the generation of a range of biaryl-based functional molecules. In contrast to the single-point connection in these products, edge-sharing fused aromatic systems have not generally been accessible from simple aryl halides via annulation cascades. Here we report a single-step synthesis of fused aromatics with a triphenylene core by the palladium-catalyze

A highly selective and divergent synthesis enables access to various molecules and has garnered broad interest from not only organic chemists but also medicinal chemists and biologists who work with chemical libraries. Since the 20th century, such divergent transformations have been achieved using transition-metal-catalyzed reactions, in which the choice of catalyst or ligand crucially affects the selectivity. Over the past several decades, photocatalysts have attracted a considerable amount of

A combination of a palladium-NHC catalyst and potassium hexamethyldisilazide enables the amination of aryl sulfides with anilines to afford a wide variety of diarylamines. The reaction conditions are versatile enough for the reaction of even bulky ortho-substituted aryl sulfides. This amination can be applied to the modular synthesis of N-aryl carbazoles from the corresponding ortho-bromothioanisoles. As aryl sulfoxides undergo extended Pummerer reactions to afford ortho-substituted aryl sulfide

Operationally simple, efficient, and widely applicable Pummerer annulations of simple phenols with ketene dithioacetal monoxides, with the aid of trifluoroacetic anhydride, have been shown to provide a variety of benzofurans having a methylthio group at the 2-position. Subsequent and newly developed nickel-catalyzed arylation at the methylthio group culminates in diversity-oriented synthesis of multisubstituted benzofurans. Our extended Pummerer annulation/cross-coupling sequence is powerful eno

Carbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon-carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewe

Nanocarbons, such as fullerenes, carbon nanotubes, and graphenes, have long inspired the scientific community. In order to synthesize nanocarbon molecules in an atomically precise fashion, many synthetic reactions have been developed. The ultimate challenge for synthetic chemists in nanocarbon science is the creation of periodic three-dimensional (3D) carbon crystals. In 1991, Mackay and Terrones proposed periodic 3D carbon crystals with negative Gaussian curvatures that consist of six- and eigh

[reaction: see text] Arylmagnesiation of unfunctionalized alkynes in the presence of catalytic amounts of chromium(II) chloride and pivalic acid proceeds with high stereoselectivity. The alkenylmagnesium intermediate reacts with various electrophiles to afford the corresponding tetrasubstituted olefins in good yields.

Cobalt(II) bromide catalyzes arylzincation of alkynes with arylzinc iodide x lithium chloride complexes in acetonitrile. The scope of the arylzincation is wide enough to use unfunctionalized alkynes, such as 6-dodecyne, as well as arylacetylenes. The inherent functional group compatibility of arylzinc reagents allows preparation of various functionalized styrene derivatives. The reaction is applicable to the efficient and stereoselective synthesis of a synthetic estrogen and its derivative.

The silver savior: Nucleophilic substitution reactions of chlorosilanes with aryl Grignard reagents have been developed which take place under silver catalysis to afford tetraorganosilanes (see scheme). This transformation is likely to be promoted by diarylargentate reagents that are generated in situ. The nucleophilic substitution reaction of chlorosilanes with organometallic reagents is a fundamental method used for forming carbon–silicon bonds.1 The reactions of chlorotriorganosilanes with or

Zinc-catalyzed nucleophilic substitution reactions of chlorosilanes with organomagnesium reagents afford various tetraorganosilanes under mild reaction conditions. The reactions can be performed on large scale and allow efficient preparation of functionalized tetraorganosilanes.

The rapid transformation of pharmaceuticals and agrochemicals enables access to unexplored chemical space and thus has accelerated the discovery of novel bioactive molecules. Because arylacetic acids are regarded as key structures in bioactive compounds, new transformations of these structures could contribute to drug/agrochemical discovery and chemical biology. This work reports carbon-nitrogen and carbon-oxygen bond formation through the photoredox-catalyzed decarboxylation of arylacetic acids

In general, aromatic cores are stable owing to their resonance energies. Different from facile peripheral modifications of aromatic cores, transforming an aromatic core into a different skeleton is ambitious and has attracted only little attention as a general synthetic method. This personal account shows our journey to inventing transformations of dibenzothiophenes into triphenylenes, carbazoles, and spirocyclic diarylfluorenes and to establishing ‘aromatic metamorphosis’ as a useful and game-c

A photoredox-catalyzed decarboxylative oxidation of arylacetic acids, which are privileged scaffolds in pharmaceuticals, is reported herein. The established method is operationally simple and a variety of substrates are applicable, providing rapid access to dehomologated bioisosteres of common pharmaceuticals.

C-H amination is the most powerful method to directly add nitrogen functionalities into a variety of arenes including biology- and materials-oriented molecules. Recent developments in aromatic C-H amination chemistry have enabled the conversion of unactivated arenes into a range of arylamine derivatives without using directing groups or excess amounts of arenes. The key for such successful transformations is the catalytic generation of nitrogen or arene radical intermediates. In this perspective