Mechanochemical generation of aryl barium nucleophiles from unactivated barium metal.

Organobarium reagents are of interest as homologues of the Grignard reagents based on organomagnesium compounds due to their unique reactivity as well as regio- and stereoselectivity. However, reactions involving organobarium reagents are less developed in comparison to reactions involving Grignard reagents due to the lack of a simple and economical synthetic method and their high reactivity. To the best of our knowledge, there is no established method for the direct synthesis of organobarium compounds from commercially available bulk barium metal and organic halides.

Solid-state mechanochemistry for the rapid and efficient synthesis of tris-cyclometalated iridium(iii) complexes.

Tris-cyclometalated iridium(iii) complexes have received widespread attention as attractive prospective materials for , organic light-emitting diodes (OLEDs), photoredox catalysts, and bioimaging probes. However, their preparation usually requires prolonged reaction times, significant amounts of high-boiling solvents, multistep synthesis, and inert-gas-line techniques. Unfortunately, these requirements represent major drawbacks from both a production-cost and an environmental perspective.

Solid-state mechanochemical cross-coupling of insoluble substrates into insoluble products by removable solubilizing silyl groups: uniform synthesis of nonsubstituted linear oligothiophenes.

Conventional solution-based organic reactions that involve insoluble substrates are challenging and inefficient. Furthermore, even if the reaction is successful, the corresponding products are insoluble in most cases, making their isolation and subsequent transformations difficult. Hence, the conversion of insoluble compounds into insoluble products remains a challenge in practical synthetic chemistry.

Efficient access to materials-oriented aromatic alkynes the mechanochemical Sonogashira coupling of solid aryl halides with large polycyclic conjugated systems.

Sonogashira coupling represents an indispensable tool for the preparation of organic materials that contain C(sp)-C(sp) bonds. Improving the efficiency and generality of this methodology has long been an important research subject in materials science. Here, we show that a high-temperature ball-milling technique enables the highly efficient palladium-catalyzed Sonogashira coupling of solid aryl halides that bear large polyaromatic structures including sparingly soluble substrates and unactivated aryl chlorides.

Synthesis of hydrosilylboronates the monoborylation of a dihydrosilane Si-H bond and their application for the generation of dialkylhydrosilyl anions.

The synthesis of a series of hydrosilylboronates the selective iridium- or nickel-catalyzed monoborylation of dihydrosilane Si-H bonds is described. The synthesized silylboronates, which bear a single Si-H bond, can be used as novel silicon nucleophiles in the presence of transition-metal catalysts or bases. The first Si{H} NMR spectroscopic evidence for the formation of (-Bu)HSiLi, generated by the reaction of (-Bu)HSi-B(pin) with MeLi, is reported as the first example of a dialkylhydorosilyl lithium species.

Air- and moisture-stable Xantphos-ligated palladium dialkyl complex as a precatalyst for cross-coupling reactions.

Although xantphos has been employed in a variety of palladium-catalyzed cross-coupling reactions, there has been little progress in developing Xantphos-ligated precatalysts. In this report, we describe a Xantphos-ligated palladium dialkyl complex that acts as a powerful precatalyst for C-N, C-S, and C-C cross-coupling reactions. This precatalyst is air- and moisture stable but can be thermally activated in the absence of external reagents.