Synthesis and Characterization of Unsymmetrical (cis-(Phosphino−arsino)ethene)tetracarbonylmolybdenum Complexes: Hydroarsination Reactions of (H3CC⋮CPPh2)Mo(CO)5 and [H2CCCH(DBP)]Mo(CO)5 and Hydrophosphination Reactions of (Ph2AsCH2C⋮CH)Mo(CO)5

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.

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Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

Tay

Yang

et al. 2019

Chemistry A European J

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Synthetic challengesh ave significantly slowed the development of the catalytic asymmetrich ydroarsination reaction despite it being ah ighly attractive CÀAs bond formation methodology.Ina ddition, there is ap oor understanding of the main reactions teps in such reactions which limit further developmenti nt he field.H erein, key intermediates of the hydroarsination reactionc atalyzed by aP CP Ni II -Cl pincer complex are presentedu pon investigating the reactionw ith DFT calculations, conductivity measurements, NMR spectros-copy,a nd catalytic screening.T he novel Ni-Cl-As interaction proposed was then contrasted against known Ni II -catalyzed hydrophosphination reactions to highlight dissimilaritiesb etweent hem even though Pa nd As share ac lose group relationship. Lastly,t he asymmetrich ydroarsination of nitroolefins was further developed to furnish al ibrary of chiral organoarsines in up to 99 %y ield and 80 % ee under mild conditions (À20 8CtoR T) between 5t o2 10 mins.[a] W.Product 5b:White solid;the ee was determined on aDaicel Chiralpak ID column with n-hexane/2-propanol = 99:1, flow = 0.8 mL min À1 ,w avelength = 254 nm;r etention times:8 .7 (minor), 9.6 min (major); 1 HNMR (CD 3 CN, 500 MHz): d = 7. 15 H, Ar), 4.98 (dd, 1H, 3 J HH = 13.1, 3 J HH = 13.1 Hz, AsCH), 4.62 (dd, 1H, 3 J HH = 13.6, 2 J HH = 3.8 Hz, NCH), 4.38 ppm (dd, 1H, 3 J HH = 12.6 Hz, 2 Conflict of interestThe authors declare no conflict of interest.

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Synthesis and Characterization of Unsymmetrical (cis-(Phosphino−arsino)ethene)tetracarbonylmolybdenum Complexes: Hydroarsination Reactions of (H₃CC⋮CPPh₂)Mo(CO)₅ and [H₂CCCH(DBP)]Mo(CO)₅ and Hydrophosphination Reactions of (Ph₂AsCH₂C⋮CH)Mo(CO)₅

Cited by 12 publications

References 16 publications

Developing the catalytic asymmetric hydroarsination reaction

Developing the catalytic asymmetric hydroarsination reaction

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

Catalytic and Mechanistic Developments of the Nickel(II) Pincer Complex‐Catalyzed Hydroarsination Reaction

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