P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

[L_C^RP((PhP)₂C₂H₄)][OTf] ( 4 a,b [OTf]) and [L_C^iPrP(PPh₂)₂][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L_C^RP(pyr)₂][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; L_C^R=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C₂H₄P(H)Ph) and Ph₂PH. A stepwise double P?N/P?P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph₂P)₂(L_C^MeP)₂][OTf]₂ ( 7 a [OTf]₂) is observed when reacting 3 a [OTf] with diphosphane P₂Ph₄. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH₃CN)₄]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph₂PPL_C^iPr)Au}₄][OTf]₄ ( 9 [OTf]₄) was unexpectedly formed as a result of a chloride‐induced P?P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH₃CN)₃][OTf]₂ (M=Cu, Ag) ( 10 [OTf]₂, 11 [OTf]₂).     

Replacement of C−O by P−O in Cyclic Acetals and Ketals

Efficiency and structural specificity earmark the reaction of phosphonium ions 1 with cyclic acetals and ketals to yield 1,3,2‐dioxaphospholanium ions 2 [Eq. (1)]. Potential applications of this reaction are in monitoring trace levels of organophosphorus esters and in developing novel carbonyl deprotection agents. R=OCH₃, CH₃; R¹=H, CH₃; R²=CH₃, C₆H₅; R³=H, CH₃.     

Oxidation of a P−C Bond under Mild Conditions

The reactivity of phosphenium dication [(Ph₃P)₂C‐P‐NiPr₂]²⁺, 1²⁺ , towards pyridine N‐oxide (O‐py) has been investigated. The resulting oxophosphonium dication [(Ph₃P)₂C(NiPr₂)P(O)(O‐py)]²⁺, 2²⁺ , was surprisingly stabilized by a less nucleophilic O‐py ligand instead of pyridine (py). This compound was then identified as an analogue of the elusive Criegee intermediate as it underwent oxygen insertion into the P?C bond through a mechanism usually observed for Baeyer–Villiger oxidations. This oxygen insertion appears to be the first example of a Baeyer–Villiger oxidation involving O‐py.     

Phosphaborenes: Accessible Reagents for the Synthesis of C−C/P−B Isosteres

Formal exchange of C=C units with isoelectronic B=N or B=P units can provide access to molecules with unique electronic or chemical properties. Herein, we report the simple solution‐phase generation of highly reactive phosphaborenes, RP=BR, and demonstrate their use for the introduction of P=B units into organic systems. Ring opening of a P−B‐containing cyclobutene isostere provided access to unique 1,4‐boraphosphabutadiene systems with conjugated main‐group multiple bonds.     

RASS‐Enabled S/P−C and S−N Bond Formation for DEL Synthesis

DNA encoded libraries (DEL) have shown promise as a valuable technology for democratizing the hit discovery process. Although DEL provides relatively inexpensive access to libraries of unprecedented size, their production has been hampered by the idiosyncratic needs of the encoding DNA tag relegating DEL compatible chemistry to dilute aqueous environments. Recently reversible adsorption to solid support (RASS) has been demonstrated as a promising method to expand DEL reactivity using standard organic synthesis protocols. Here we demonstrate a suite of on‐DNA chemistries to incorporate medicinally relevant and C?S, C?P and N?S linkages into DELs, which are underrepresented in the canonical methods.     

Silver‐Catalyzed Oxidative C(sp3)−P Bond Formation through C−C and P−H Bond Cleavage

The silver‐catalyzed oxidative C(sp³)−H/P−H cross‐coupling of 1,3‐dicarbonyl compounds with H‐phosphonates, followed by a chemo‐ and regioselective C(sp³)−C(CO) bond‐cleavage step, provided heavily functionalized β‐ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional‐group tolerance, and exclusive selectivity.     

Facile P−C/C−H Bond‐Cleavage Reactivity of Nickel Bis(diphosphine) Complexes

Unusual cleavage of P?C and C?H bonds of the P₂N₂ ligand, in heteroleptic [Ni(P₂N₂)(diphosphine)]²⁺ complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P‐tridentate coordination mode. The structures of both the heteroleptic [Ni(P₂N₂)(diphosphine)]²⁺ complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P?C/C?H bond cleavage, which involves C?H bond cleavage, hydride rotation, Ni?C/P?H bond formation, and P?C bond cleavage.     

Reversible Silylene Insertion Reactions into Si−H and P−H σ‐Bonds at Room Temperature

Phosphine‐stabilized silylenes react with silanes and a phosphine by silylene insertion into E?H σ‐bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step.     

Reactivity of the >P‐O− nucleophiles toward arylmethyl chloride systems*†

The reactions of sodium dimethyl and diisopropyl phosphite, as well as dibenzylphosphinite with 4‐nitrobenzyl chloride, 9‐chlorofluorene, and diphenylchloromethane were studied in detail by the isolation and identification of all the products, and the examination of the effects of the solvents on the product distribution. The results of the performed experiments are compatible with the proposed mechanism: a >P‐O⁻ anion acts toward an arylmethyl chloride as a base and abstracts a proton to form a carbanion, which can then participate in the SET processes to produce carbon‐centered radicals. Additionally, the >P‐O⁻ reagent can act as a carbon‐centered radical trap if it is present in a high enough concentration. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 431–439, 1999     

P−B Desulfurization: An Enabling Method for Protein Chemical Synthesis and Site‐Specific Deuteration

Cysteine‐mediated native chemical ligation is a powerful method for protein chemical synthesis. Herein, we report an unprecedentedly mild system (TCEP/NaBH₄ or TCEP/LiBEt₃H; TCEP=tris(2‐carboxyethyl)phosphine) for chemoselective peptide desulfurization to achieve effective protein synthesis via the native chemical ligation–desulfurization approach. This method, termed P−B desulfurization, features usage of common reagents, simplicity of operation, robustness, high yields, clean conversion, and versatile functionality compatibility with complex peptides/proteins. In addition, this method can be used for incorporating deuterium into the peptides after cysteine desulfurization by running the reaction in D₂O buffer. Moreover, this method enables the clean desulfurization of peptides carrying post‐translational modifications, such as phosphorylation and crotonylation. The effectiveness of this method has been demonstrated by the synthesis of the cyclic peptides dichotomin C and E and synthetic proteins, including ubiquitin, γ‐synuclein, and histone H2A.     

Oxidative P−P Bond Addition to Cobalt(−I): Formation of a Low‐Spin Cobalt(III) Phosphanido Complex

The first homoleptic cobalt phosphanido complex [K(thf)₄][Co{1,2‐(Pt Bu₂)₂C₂B₁₀H₁₂}₂] ( 1 ) was prepared by an unprecedented oxidative P−P bond addition of an ortho ‐carborane‐substituted 1,2‐diphosphetane to cobalt(−I) in [K(thf)_0.2][Co(η⁴‐cod)₂)] (cod=1,5‐cycloctadiene). Compound 1 is a rare distorted tetrahedral 3d⁶ complex with a low‐spin ground state configuration. Magnetic measurements revealed that the complex is diamagnetic between 2 to 270 K in the solid state and at 298 K in [D₈]THF solution. Based on DFT calculations, the unusual singlet ground state is caused by the strong σ‐donor and moderate π‐donor properties of the bis(phosphanido) ligand.     

Access to P‐ and Axially Chiral Biaryl Phosphine Oxides by Enantioselective CpxIrIII‐Catalyzed C−H Arylations

An enantioselective C?H arylation of phosphine oxides with o‐quinone diazides catalyzed by an iridium(III) complex bearing an atropchiral cyclopentadienyl (Cp^x) ligand and phthaloyl tert‐leucine as co‐catalyst is reported. The method allows access to a) P‐chiral biaryl phosphine oxides, b) atropo‐enantioselective construction of sterically demanding biaryl backbones, and also c) selective assembly of axial and P‐chiral compounds in excellent yields and diastereo‐ and enantioselectivities. Enantiospecific reductions provide monodentate chiral phosphorus(III) compounds having structures and biaryl backbones with proven importance as ligands in asymmetric catalysis.     

A Plasma‐Triggered O−S Bond and P−N Junction Near the Surface of a SnS2 Nanosheet Array to Enable Efficient Solar Water Oxidation

A photoelectrochemical (PEC) cell can split water into hydrogen and oxygen with the assistance of solar illumination. However, its application is still limited by excessive bulk carrier recombination and sluggish surface oxygen evolution reaction (OER) kinetics. Taking SnS₂ as an example, a promising layered optoelectronic semiconductor, Ar plasma treatment strategy was used to introduce a SnS/SnS₂ P?N heterojunction and O?S bond near the surface of a SnS₂ nanosheet array, simultaneously increasing the separation efficiency of photogenerated electron–hole pairs in the bulk and lowering the OER overpotential at the surface. The onset potential of the plasma‐treated SnS₂ nanosheet array shifts negatively to 0.16 V, and the photocurrent density at 1.23 V vs. RHE boosts to 2.15 mA cm^?2, which is 7 times that of pristine SnS₂. This work demonstrates a facile plasma treatment strategy to modulate the energy band structure and surface chemical states for improved PEC performance.