C−As Bond Formation Reactions for the Preparation of Organoarsenic(III) Compounds

Abstract

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.

Chemical synthesis of the organoarsenical antibiotic arsinothricin

“…A variety of synthetic protocols are being developed for novel organoarsenicals. 4,5 The structures of the new aromatic arsenical metabolites discovered in chicken liver were confirmed by chemical synthesis. 6 …”

“…A variety of synthetic protocols are being developed for novel organoarsenicals. 4,5 The structures of the new aromatic arsenical metabolites discovered in chicken liver were conrmed by chemical synthesis. 6 Recently a new arsenic-containing compound, arsinothricin [2-amino-4-(hydroxymethylarsinoyl)butanoic acid, AST (1); Scheme 1], was shown to be synthesized by the rice rhizosphere bacterium Burkholderia gladioli GSRB05.…”

Practical Syntheses and Luminescent Properties of Arene‐substituted Arsines

“…Despite these significant advantages over the other group 15 elements, the experimental study on organoarsenic compounds had been severely restricted by a lack of practical synthetic methods for long time. That is, the traditional synthetic routes require volatile and toxic precursors such as arsenic chlorides and hydrides [5] . To address this issue, we have developed various synthetic routes for organoarsenic compounds [6] .…”

“…That is, the traditional synthetic routes require volatile and toxic precursors such as arsenic chlorides and hydrides. [5] To address this issue, we have developed various synthetic routes for organoarsenic compounds. [6] Among the accessible compounds, arsole, in which the sp 3 carbon of cyclopentadiene is substituted by an arsenic atom, has been particularly studied as arsenic-fused πconjugated systems; e. g., triarylarsoles, [7] pentaarylarsoles, [8] dithienoarsoles, [9] benzoarsoles, [10] and arsafluorenes.…”

“…[7] On the other hand, as limited examples, 9-phenyl-9arsafluorene [6b] and dithieno [3,4-b : 3',4'-d]arsole [9c] structures can give phosphorescence at 77 K (Figure 1b). The small conjugation systems such as biphenyl (arsafluorene) and [5]radialene (dithieno [3,4-b : 3',4'-d]arsole) backbones, which might reduce the k r from the S 1 states, are favorable to utilize the heavy atom effect of the arsenic atom, leading to phosphorescence. It is important to produce arsenic-driven phosphorescence because the novel molecular design for phosphorescence dyes is a promising tool to develop advanced organic materials.…”