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Potential widespread applications of organoarsenic chemistry have been limited by the inherent lack of safe and effective As−C bond formation reactions. Several alternative reagents and methods have been developed in the last few decades to address the hazards and drawbacks associated with traditional arsenic synthetic strategies. Herein, this minireview summarizes the advances made in nucleophilic, electrophilic, radical and metal‐mediated As(III)−C bond formations while specifically highlighting the behavior of arsenic synthons with various well‐established reagents (eg. Grignard reagents, organolithium compounds, organometallic reagents, radical initiators and Lewis/Brønsted bases). Avenues for asymmetric synthesis are also discussed, as are recent advances in organoarsenic chemistry suggesting that arsines exhibit novel reactivities independent from that of other relatively more well explored Group V cogeners. [ABSTRACT FROM AUTHOR]

Synthetic challenges have significantly slowed the development of the catalytic asymmetric hydroarsination reaction despite it being a highly attractive C−As bond formation methodology. In addition, there is a poor understanding of the main reaction steps in such reactions which limit further development in the field. Herein, key intermediates of the hydroarsination reaction catalyzed by a PCP NiII‐Cl pincer complex are presented upon investigating the reaction with DFT calculations, conductivity measurements, NMR spectroscopy, and catalytic screening. The novel Ni–Cl–As interaction proposed was then contrasted against known NiII‐catalyzed hydrophosphination reactions to highlight dissimilarities between them even though P and As share a close group relationship. Lastly, the asymmetric hydroarsination of nitroolefins was further developed to furnish a library of chiral organoarsines in up to 99 % yield and 80 % ee under mild conditions (−20 °C to RT) between 5 to 210 mins. [ABSTRACT FROM AUTHOR]