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

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.

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

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.

Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination.

Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(ii) pincer complex adept at generating enantioenriched phosphines was examined in the asymmetric hydroarsination reaction. Under distinct conditions, tertiary phosphines and arsines were generated in excellent yields (P: 96%, As: 91%) and ees (P: 90%, As: 85%). While secondary arsine reagents were not direct substitutes for the analogous phosphines, important parameters were identified which increased yield and ee of the hydroarsination reaction. Unlike the PCP-PdOAc pincer complex commonly used for hydrophosphinations, hydroarsination reactions involved a PCP-PdCl catalyst with 10 equiv. of CsF for optimal performance. Notable differences between the two reactions and their workup procedures were highlighted to guide further developments in the field. Lastly, respective mechanisms were proposed and contrasted for the activation of HEPh2 (E = P, As).

Nickel catalyzed enantioselective hydroarsination of nitrostyrene.

A catalytic asymmetric hydroarsination reaction of an activated alkene viz. (E)-nitrostyrene was developed using chiral PCP Pt-, Pd- and Ni-pincer complexes as catalysts. The corresponding chiral tertiary arsine adduct was obtained in ees of up to 80% under mild reaction conditions using the PCP Ni-Cl pincer catalyst. The arsine adduct was furnished with catalyst loadings of 1-5 mol% and the reaction duration ranging from <5 min to 180 min. The subsequent coordination of the hydroarsination product to gold(i) chloride allowed for the confirmation of the stereochemistry of the arsine adduct via crystallographic analysis.

Mechanistic insights into the role of PC- and PCP-type palladium catalysts in asymmetric hydrophosphination of activated alkenes incorporating potential coordinating heteroatoms.

The impact of the structural attributes of chiral PC- and PCP-palladium catalysts was investigated in the asymmetric hydrophosphination of various heterocycle-functionalized enone substrates. Due to the architecture of the catalysts, they are confronted with potential catalyst deactivation arising from the coordination of the electron-rich heteroatoms (P, O, N and S) to the metal center. A systematic variation of the location and identity of the heteroatoms demonstrated the impact of structural modifications on the substrates, which have a significant influence on both yields (16-99%) and enantioselectivities (0-99%). A detailed discussion on the distinct catalytic mechanisms (intra- vs. inter-molecular addition) provides important information to explain the results obtained.

The synthesis and efficient one-pot catalytic "self-breeding" of asymmetrical NC(sp(3))E-hybridised pincer complexes.

Cyclopalladation of the pyridyl-substituted chiral phosphine sulfide (N-P=S) and oxide (N-P=O) compounds afforded the asymmetric N-C(sp(3))*-S and N-C(sp(3))*-O pincer complexes. When applied as catalysts in asymmetric hydrophosphination, the newly developed aliphatic pincer catalyst could be recycled over three runs and obtained in large quantities via a one-pot "self-breeding" catalytic protocol.

Computational and carbon-13 NMR studies of Pt-C bonds in P-C-P pincer complexes.

A (13)C{(1)H} NMR based investigation was conducted to examine the electronic properties of C(aryl)-M bonds and their trans influence in P-C(aryl)-P pincer complexes. A series of structurally related platinum pincer complexes were rationally designed and their corresponding (13)C-(195)Pt coupling constants were systematically examined. By methodical substitution of the ligand trans to the organometallic C(aryl)-Pt bond, this study revealed the significant influence of the ligands on the nature of the C(aryl)-M bonds. The single crystal X-ray analysis of the complexes and computational studies further confirmed the observations that the C-M bond exhibits significant π-character.