Unexpected rapid <i>P</i>-stereomutation of phosphine oxides catalysed by chlorophosphonium salts

Al-Sulaimi, Sulaiman; Rajendran, Kamalraj; Nikitin, Kirill; Gilheany, Declan G.

doi:10.1039/d3cc03719c

Cited by 3 publications

(1 citation statement)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Very recently, Nikitin, Gilheany, and co-workers proposed that the oxodiphosphonium P−O−P species was a key intermediate generated in the chloro-phosphonium catalyzed chiral phosphine oxide racemization. 25 To investigate whether an oxodiphosphonium P−O−P species was the intermediate in our system, intramolecular oxodiphosphonium 12 was synthesized (Scheme 7). The 31 P NMR chemical shift of 12 lies at 74.3 ppm, which aligns with that of the Hendrickson's reagent (δ( 31 P) = 75 ppm).…”

Section: ■ Introductionmentioning

confidence: 99%

Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications

Xue,

Zhang,

Huan

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Controlling product selectivity in successive reactions of the same type is challenging owing to the comparable thermodynamic and kinetic properties of the reactions involved. Here, the synergistic interaction of the two phosphoryl groups in bisphosphine dioxides (BPDOs) with a bromo-phosphonium cation was studied experimentally to provide a practical tool for substrate−catalyst recognition. As the eventual result, we have developed a phosphonium-catalyzed monoreduction of chiral BPDOs to access an array of synthetically useful bisphosphine monoxides (BPMOs) with axial, spiro, and planar chirality, which are otherwise challenging to synthesize before. The reaction features excellent selectivity and impressive reactivity. It proceeds under mild conditions, avoiding the use of superstoichiometric amounts of additives and metal catalysts to simplify the synthetic procedure. The accessibility and scalability of the reaction allowed for the rapid construction of a ligand library for optimization of asymmetric Heck-type cyclization, laying the foundation for a broad range of applications of chiral BPMOs in catalysis.

show abstract

Section: ■ Introductionmentioning

confidence: 99%

Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications

Xue,

Zhang,

Huan

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Mahata,

Kumari,

Chakraborty

2024

ChemCatChem

View full text Add to dashboard Cite

While phosphamides are well flame retardants, herein a mesoporous polyphosphamide (p‐PPA) with an accessible average pore diameter of <10 nm and a surface area of 1.773 m2/g has been synthesized via condensation of 1,3‐diamino benzene (DAB) and phenyl phosphinic dichloride (PPDC). 31P, 13C CP‐MAS NMR, Raman spectra, and X‐ray photon spectroscopic (XPS) characterizations confirm the presence of ‐{PV(O)‐NH}‐ in the repeating unit of the p‐PPA that is further used as a catalytic mediator to perform the Appel reaction i.e., conversion of alcohols to halides with a broad substrate scope and high TON (561). The heterogeneity of p‐PPA allows easy recovery of organic halides and recycling of the catalyst many times. Mesoporous p‐PPA have further given a scope to perform shape‐selective conversion of primary alcohols with linear alkyl chain (1‐dodecanol) while low conversions for the bulky secondary (cyclo‐hexanol) and tertiary alcohol (tert‐butanol) are observed. Perhaps, the phosphamide units present inside the porous sites are non‐preferable site for bulkier alcohols, as evident from the competitive experiments. A comparatively less catalytic conversion obtained with an analogous non‐porous n‐PPA, made of tris(2‐aminoethyl)amine (TREN) linker, highlights the role of porosity in p‐PPA to enhances the accessibility of numerous ‐{PV(O)‐NH}‐ reactive units to increase the TON.

show abstract

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

Vijai Anand,

Perinbanathan,

Singh

et al. 2024

ChemCatChem

View full text Add to dashboard Cite

Phosphine oxides are an interesting class of compounds possessing tetracoordinate and pentavalent phosphorus atoms and have been employed in a wide range of applications including reagents in organic synthesis, metal extractants, flame retardants, pharmaceuticals, and bioactivity studies. Among all, the degree of basicity of phosphoryl oxygen driven by the nature of substituents influences the electronic properties of the central metal in a complex toward the diversified catalytic processes. Further, the presence of heteroatoms adjacent to the central phosphorus atom enhances the nucleophilicity of the phosphoryl oxygen atom. In view of this, the present review covers the past two decades of remarkable catalytic versatility of P=O‐based metal complexes and describes the governing factors influencing the structural properties and the resultant coordination behavior. Interestingly, some of the P=O bond distances of metal complexes are either longer or shorter compared to their free ligands, indicating the catalytic activity. These complexes can effectively catalyze a wide range of chemical reactions including polymerizations, C‐C and Si‐C bond activations, oxidation, reduction, hydroformylation, hydrophosphination, hydrogenation and cyclization reactions. Furthermore, this review emphasizes the impact of substituents, solvents, additives, light, and temperature on the catalytic efficiency.

show abstract

Unexpected rapid P-stereomutation of phosphine oxides catalysed by chlorophosphonium salts

Abstract: Crack the CPS whip. Stereochemical inversion of P-chiral phosphine oxides is difficult. Fast-acting chlorophosphonium salts help to spur-up this commonly very slow process.

Cited by 3 publications

References 39 publications

Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications

Phosphonium-Catalyzed Monoreduction of Bisphosphine Dioxides: Origin of Selectivity and Synthetic Applications

Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

Contact Info

Product

Resources

About