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The first total synthesis of anti-inflammatory cyclic peptide fanlizhicyclopeptide B based on the Mitsunobu reaction is reported. The pre-made Fmoc-Tyr-OAllyl building block was coupled to the Wang resin via the Mitsunobu reaction catalyzed by triphenylphosphine and diethyl azodicarboxylate. After the remaining amino acids were assembled, macrocyclization was realized on solid support. Finally, the crude product was cleaved from resin and then purified by preparative reverse-phase high-performance liquid chromatography (RP-HPLC) to provide the pure target fanlizhicyclopeptide B.

Despite intensive studies on the synthesis of 3-formylindoles, it is still highly desirable to develop efficient methods for the formylation of indoles, due to the shortcomings of the reported methods, such as inconvenient operations and/or harsh reaction conditions. Here, we describe a Ph3P/ICH2CH2I-promoted formylation of indoles with DMF under mild conditions. A Vilsmeier-type intermediate is readily formed from DMF promoted by the Ph3P/ICH2CH2I system. A one-step formylation process can be applied to various electron-rich indoles, but a hydrolysis needs to be carried out as a second step in the case of electron-deficient indoles. Convenient operations make this protocol attractive.

The bungeanools are a family of alkamide natural products isolated from the pericarps of Zanthoxylum bungeanum (Sichuan pepper), and they are structurally related to the sanshools. While the sanshools, especially hydroxy-α-sanshool, have been studied in a variety of contexts, research regarding the bungeanools has been much more limited. To facilitate their study, we have developed stereoselective syntheses of all four members of this family of compounds by using flexible routes that are also amenable to the synthesis of analogues. The key transformation in the syntheses was the stereoselective triphenylphosphine/phenol-catalyzed isomerization of an alkynoate to the corresponding conjugated E,E-dienoate.

An efficient triphenylphosphine oxide-catalyzed amidation and esterification for the rapid synthesis of a series of dipeptides, amides, and esters is described. This reaction is applicable to challenging couplings of hindered carboxylic acids with weakly nucleophilic amines or alcohols, giving the products in good yields (67-90%) without racemization. This system employs the highly reactive intermediate Ph3PCl2 as the activator of the carboxylate in a catalytic manner and drives the reaction to completion in a short reaction time (less than 10 min).

We compare three methods for quantitatively distinguishing the location of noble metal (NM) particles in mesopores from those found on the external support surface. MCM-41 and SBA-15 with NM located in mesopores or on the external surface were prepared and characterized by TEM. 31 P MAS NMR spectroscopy was used to quantify arylphosphines in complexes with NM. Phosphine/NM ratios drop from 2.0 to 0.2 when increasing the probe diameter from 1.08 to 1.54 nm. The reaction between NM and triphenylphosphine (TPP) within 3.0 nm MCM-41 pores takes due to confinement effects multiple weeks. In contrast, external NM react with TPP instantly. A promising method is filling the pores by using the pore volume impregnation technique with tetraethylorthosilicate (TEOS). TPP loading revealed that 66 % of NMs are located on the external surface of MCM-41. The pore filling method can be used in association with any probe molecule, also for the quantification of acid sites.

Described herein is the development of a continuous flow, solid-phase triphenylphosphine (PS-PPh3) assisted protocol to facilitate the in situ coupling of reciprocal pairs of halogen and carbonyl functionalised molecular pairs by a Wittig olefination within 15 mins. The protocol entails injecting a single solution (1 : 1 CHCl3 : EtOH) containing the halogenated and carbonyl-based substrates into a continuously flowing stream of CHCl3 : EtOH (1 : 1), passed through a fixed bed of K2CO3 and PS-PPh3. With advancement to the previous PS-PPh3 coupling procedures, the method employs a traditional polystyrene-based immobilisation matrix, the substrate scope of the protocol extended to substituted ketones, secondary alkyl chlorides, and an unprotected maleimide scaffold.

A new efficient synthesis of polysubstituted pyrazin-2(1H)-ones via the sequential Ugi/Staudinger/aza-Wittig/isomerization reaction has been developed. The four-component Ugi reactions of arylglyoxals 1, primary amines 2, α-azidovinyl acids 3, and isocyanides 4 produced the azides 5, which were treated with triphenylphosphine to give pyrazin-2(1H)-ones 6 in good yields through domino Staudinger/aza-Wittig/isomerization reactions.

Electron-rich triarylphosphines, namely 4-(methoxyphenyl)diphenylphosphine (MMTPP) and tris(4-trimethoxyphenyl)phosphine (TMTPP), outperform commonly used triphenylphosphine (TPP) in catalyzing oxa-Michael additions. A matrix consisting of three differently strong Michael acceptors and four alcohols of varying acidity was used to assess the activity of the three catalysts. All test reactions were performed with 1 mol % catalyst loading, under solvent-free conditions and at room temperature. The results reveal a decisive superiority of TMTPP for converting poor and intermediate Michael acceptors such as acrylamide and acrylonitrile and for converting less acidic alcohols like isopropanol. With stronger Michael acceptors and more acidic alcohols, the impact of the more electron-rich catalysts is less pronounced. The experimental activity trend was rationalized by calculating the Michael acceptor affinities of all phosphine–Michael acceptor combinations. Besides this parameter, the acidity of the alcohol has a strong impact on the reaction speed. The oxidation stability of the phosphines was also evaluated and the most electron-rich TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar masses of about 1200 g/mol at room temperature are accessible. Polymerizations carried out at 80 °C resulted in macromolecules containing a considerable share of Rauhut–Currier-type repeat units and consequently lower molar masses were obtained.

Three chlorido(triphenylphosphine)ruthenium(II) dithiocarbamate complexes - [RuCl(PPh3)3(Mbzdtc)] 1, [RuCl(PPh3)3(Ppipdtc)] 2, and [RuCl(Ph3)3(Mordtc)] 3 with Mbzdtc = N-methylphenyldithiocarbamate...

An addition of the Morita—Baylis—Hillman (MBH) carbonates to adamantane-containing isothiocyanates was studied. The MBH carbonates react with 1-(4-isothiocyanatophenyl)-adamantane in the presence of triphenylphosphine to give 5-aryl-substituted adamantane-containing 2-amino-4-methoxycarbonylthiophenes in 31–59% yields, while 1- and 2-isothio-cyanatoadamantanes were found unreactive in this reaction.

Highly convergent synthesis of angiotensin II receptor blockers has been accomplished by means of late-stage C–H arylation using functionalized aryl bromides. C–H arylation of 1-benzyl-5-phenyl-1H-tetrazole with aryl bromides carrying methyl 2-ethoxybenzimidazole-7-carboxylate unexpectedly provided coupling products where ethyl group was migrated from oxygen to nitrogen atom. The O-to-N ethyl migration was completely suppressed by the use of N-pivaloyl-l-valine rather than the combined use of triphenylphosphine and sodium mesitylenesulfonate to result in the preferential formation of a key intermediate of candesartan cilexetil. In contrast, when an aryl bromide having ethyl 4-(1-hydroxy-1-methylethyl)-2-propylimidazole-5-carboxylate was employed, the C–H arylation proceeded smoothly to provide a late-stage intermediate, which rapidly led to olmesartan medoxomil in 3 steps.

In this work, the method of combining the various ligands with Raney Ni in continuous flow is proposed, in which triphenylphosphine (TPP) can effectively improve the chemical selectivity of anilines prepared by nitroarenes hydrogenation and maintain high activity. Meanwhile, through the analysis of ICP, FT-IR, XRD, and EDS, we have concluded that the low degree of complexation and the uniform distribution of TPP are presumed be the keys to high selectivity and activity. TPP/Raney Ni exhibits excellent tolerance to halogens and unsaturated functional groups in the continuous flow system of nitroarenes hydrogenation. Furthermore, the practicability of the continuous flow system was tested.

Novel highly substituted zwitterionic furans were generated through the in situ formation of phosphonium salts. Firstly, intermediate salts were obtained via nucleophilic attack of Huisgen zwitterion to 3-cyanochromones. Finally, these intermediate salts underwent a proton migration, intramolecular cyclization, and ring-opening reaction to convert to the target products. The synthesized furans could be easily purified without traditional purification techniques (chromatography and recrystallization).

The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.

In this work, synthesis of pyrido[2,1-a]isoquinolines and pyrido[1,2-a]quinolines in excellent yield using multicomponent reactions of isoquinoline, methyl malonyl chloride, alkyl bromides, and tri...

A highly efficient, reusable, catalytic system of Heck and Suzuki cross-coupling reactions was observed for an inexpensive copper complex dispersed in ethyl-methyl imidazolium hexafluorophosphate medium, [EMIM]PF6. The reaction conditions were optimized by studying the effects of temperature, catalyst concentration, solvent, and time. This method functions for a variety of substrates towards the cross-coupling reactions. Most notably, the catalyst – ionic liquid mixture was easily recoverable and reused six times without much loss in the catalytic activity, causing a notably very low impact on the environment.

Two new Ni(II) complexes, bis(N-(pyrrol-2-ylmethyl)-N-(2-phenylethyl)dithiocarbamato-S,S′)nickel(II) (1) and (N-(pyrrol-2-ylmethyl)-N-(2-phenylethyl)dithiocarbamato-S,S′)(thiocyanato-κN)(triphenylphosphine)nickel(II) (2) were synthesized and characterized by elemental analysis, IR, UV-vis and NMR spectroscopy. IR and 13C{1H} NMR spectra of both complexes suggest that the dithiocarbamate ligands interact with metal ion as bidentate ligands. Electron spectra reveal square planar geometry for both complexes. A detailed description of crystal structure, DFT calculations and Hirshfeld surface analysis of 2 is also reported. The structure determination of 2 by X-ray crystallography confirmed the presence of four coordinated Ni(II) with distorted square planar geometry. The optimized geometry, HOMO – LUMO energy gap, molecular electrostatic potential (MEP) map and global reactivity descriptors were obtained using DFT calculations. The geometric parameters calculated for 2 using the DFT method are in good agreement with those obtained from single crystal X-ray structure determination. One of the interesting structural features of 2 are the obvious intramolecular and intermolecular C-H···Ni anagostic interactions. Hirshfeld surface analysis showed the nature of intermolecular contacts. The largest contribution to the crystal packing is from H···H interactions.

A manganese-catalyzed N-alkylation reaction of amines with alcohols via hydrogen autotransfer strategy has been demonstrated. The developed practical catalytic system including an inexpensive, nontoxic, commercially available MnCl2 or MnBr(CO)5 as the metal salt and triphenylphosphine as a ligand provides access to diverse aromatic, heteroaromatic, and aliphatic secondary amines in moderate-to-high yields. In addition, this operationally simple protocol is scalable to the gram level and suitable for synthesizing heterocycles such as indole and resveratrol-derived amines known to be active for Alzheimer's disease.

A [6 + 3] annulation reaction of Morita-Baylis-Hillman carbonates and dicyanoheptafulvene is accomplished by employing commercially available triphenylphosphine as the Lewis base catalyst. A spectrum of densely functionalized bicyclo[4.3.1]decane architectures are efficiently constructed with exclusive diastereoselectivity and good yield (up to 95%).

The development of “metal-free” catalyst systems with high efficiency for the ring-opening polymerization (ROP) of epoxides, providing polyethers with controlled molecular weights and dispersity as well as the desired main-chain sequence, is crucially required. In this paper, we present a binary catalyst system, in which triphenylboroxin (TPBX) is employed as a catalyst in conjunction with bis-(triphenylphosphine)iminium chloride (PPNCl) as the initiator, for the ROP of epoxides to precisely synthesize polyethers. The binary TPBX/PPNCl system exhibits good activity under mild conditions, yielding polyethers with predictable molecular weights and low dispersity (Đ < 1.25). Of importance is that the ROP of epoxides mediated by the binary system shows a living polymerization character, allowing for the synthesis of multi-block polyethers. In addition, the synthesis of propylene oxide/ethylene oxide copolyethers with a random structure is achieved. Furthermore, on the basis of the kinetics study, a bimolecular TPBX cooperatively catalyzed mechanism is proposed and verified by density functional theory (DFT) calculations.

2-Trifluoromethacrylic acid (MAF) is a peculiar fluorinated functional monomer. Though it is known to polymerise via CC bond cleavage under anionic initiation, its oxa-Michael addition polymerisation afforded polyesters bearing trifluoromethyl side groups. This oxa-Michael addition was attempted in the presence of radical (peroxides), basic (amines and phosphines) and acidic (AlCl3, triflic acid, and p-toluenesulfonic acid) reactants and catalysts which led to the formation of oligomers with various yields (up to 57%) and molar masses (up to 2200 g mol−1). The obtained polyesters were characterised by GC/MS, IR, 19F NMR, 1H NMR and 13C NMR spectroscopy techniques and MALDI-TOF, and their thermal properties were determined by thermogravimetric analysis and differential scanning calorimetry. Triphenylphosphine and piperidine led to the highest degree of polymerization DPn (up to the 16th adduct) with a degradation temperature of about 200 °C. The glass transition temperatures (Tg) were −59 and −46 °C for the MAF bisadduct (diMAF) and oligoMAF, respectively. Such oligomers were hydrophobic, evidenced by a water contact angle measurement of 107°, showing that the contribution of the trifluoromethyl group was higher than that of the ester function.

We herein report a chemo- and regioselective 6-exo-dig catalytic cyclization of Ugi adducts N-substituted 2-alkynamides to access functionalized morpholinone glycoconjugates in the presence of triphenylphosphine. This array allows an interesting multicomponent access to a library of functionalized morpholinone glycoconjugates under mild reaction conditions with regeneration of catalyst triphenylphosphine, supported by 31P nuclear magnetic resonance studies. Density functional theory shows the 6-exo-dig oxocyclization pathway is preferred, which supports our experimental observation.

In this work, the synthesis of 1,3,4-oxadiazole derivatives using triphenylphosphine dibromide/triethylamine (Ph3P/Br2/Et3N), 1,2-bis(diphenylphosphaneyl)ethane/2Br2/Et3N, and nano-silica-anchored PPh2/Br2/Et3N systems is described. The method allows the preparation of 1,3,4-oxadiazoles with a broad substrate scope from easily accessible materials.

The alkylation of 5,5′-diaryl-2,2′-biimidazole-1,1′-diols with an equimolar amount of methyl iodide gave the corresponding N-methyl derivatives, and the reaction with 3 equiv of methyl iodide afforded alkylation products at the nitrogen atom and both hydroxy groups. 5,5′-Diaryl-1H,1′H-2,2′-biimidazoles were obtained by treatment of the title compounds with triphenylphosphine.

The intramolecular cross-linking of single polymer chains can form single-chain nanoparticles (SCNPs), which have many applications. In this study, styrenic copolymers with pendent triphenylphosphine as the coordination site for platinum ions (Pt(II)) and benzocyclobutene as the latent reactive groups are synthesized. Triphenylphosphine groups in the chains can coordinate Pt(II) and aid slight single-chain folding in dilute solution. The intramolecular cross-linking caused by the ring-open reaction of benzocyclobutene completes the single-chain collapse and forms stable SCNPs in dilute solution. Pt(II) embedded in SCNPs can be further reduced to platinum atoms (Pt(0)). Pt(0) steadily and atomically dispersed in SCNPs exhibits better catalytic properties than normal polymer carried platinum particles do for the reduction of p-nitrophenol to p-aminophenol.

The two independent and NN^ coordination sites of a newly synthesized bis[2-(hydroxyphenyl)-1,2,4-triazole] platform have been exploited to prepare four monometallic neutral ()PtII complexes carrying DMSO, pyridine, triphenylphosphine, or N-heterocyclic carbene as the fourth ligand. Then, the second NN^ coordination site was used to introduce an IR-active rhenium tricarbonyl entity, affording the four corresponding heterobimetallic neutral PtII /ReI complexes, as well as a cationic PtII /ReI derivative. X-ray crystallographic studies showed that distortion of the organic platform occurred to accommodate the coordination geometry of both metal centers. No ligand exchange or transchelation occurred upon incubation of the PtII complexes in aqueous environment or in the presence of FeIII , respectively. The antiproliferative activity of the ligand and complexes was first screened on the triple-negative breast cancer cell line MDA-MB-231. Then, the IC50 values of the most active candidates were determined on a wider panel of human cancer cells (MDA-MB-231, MCF-7, and A2780), as well as on a nontumorigenic cell line (MCF-10A). Low micromolar activities were reached for the complexes carrying a DMSO ligand, making them the first examples of highly active, but hydrolytically stable, PtII complexes. Finally, the characteristic mid-IR signature of the {Re(CO)3 } fragment in the Pt/Re heterobimetallic complexes was used to quantify their uptake in breast cancer cells.

A diastereoselective hydroalkynylation of terminal alkynes to form the head‐to‐head dimerization products by two different cobalt‐phosphine catalyst system is reported. The use of the bidentate ligand dppp and additional triphenylphosphine led to the selective formation of the (E)‐1,3‐enynes (E:Z>99:1) in good to excellent yields, while the tridentate ligand TriPhos led to the corresponding (Z)‐1,3‐enynes in moderate to good yields with excellent stereoselectivities (up to E:Z=1:99). Both pre‐catalysts are easy to handle, because of their stability under atmospheric conditions. The optimized reaction conditions were identified by the Design of Experiments (DoE) approach, which has not been used before in cobalt‐catalysed reaction optimisation. DoE decreased the number of required reactions to a minimum., Cobalt catalysis at a crossroad: The choice of the ligands in a cobalt‐catalysed hydroalkynylation of terminal alkynes is decisive to form the dimerization products in a diastereoselective fashion. The (E)‐1,3‐enynes are formed in good to excellent yields and outstanding selectivities (E:Z>99:1), while the corresponding (Z)‐1,3‐enynes were isolated in moderate to good yields with excellent stereoselectivities (up to E:Z=1:99).

The synthesis and characterization of a series of novel cationic multimetallic transition-metal complexes based on the cationic phosphine ligand (η6-diphenylphosphinobenzene)(η5-cyclopentadienyl)ir...

A practical and efficient method to synthesize thiocarbamyl fluorides and isothiocyanates from amines with trifluoromethanesulfonyl chloride was developed. In the presence of the reducing agent triphenylphosphine and sodium iodide, thiocarbamyl fluorides and isothiocyanates were synthesized from secondary/primary amine in moderate to excellent yields, respectively. A broad scope of substrates and good functional group compatibility were observed.

The synthesis of phosphine‐based functional covalent organic frameworks (COFs) has attracted great attention recently. Herein, we present two examples of triphenylphosphine‐based COFs (termed P‐COFs) with well‐defined crystalline structures, high specific surface areas, and good thermal stability. Furthermore, rhodium catalysts with these P‐COFs as support material show high turnover frequency for the hydroformylation of olefins, as well as excellent recycling performance. This work not only extends the phosphine‐based COF family, but also demonstrates their application in immobilizing homogeneous metal‐based (e.g., Rh‐phosphine) catalysts for application in heterogeneous catalysis., A turn up for turnover: Two triphenylphosphine‐based COFs (P‐COFs) that stack in an eclipsed AA manner and have high crystallinity, high specific surface areas and good thermal stability have been synthesized. The application of these P‐COFs in phosphorus coordination catalysis was demonstrated by the hydroformylation of olefins over supported Rh/P‐COFs catalysts, which showed high turnover frequencies and excellent recycling.

A photocatalyzed intramolecular cyclization is developed for the synthesis of fluorenones. In this photoredox reaction, triphenylphosphine is used as an inexpensive and effective deoxygenative reagent for biarylcarboxylic acids to give acyl radicals, which quickly undergo intramolecular radical cyclization. Reactions in the presence of air and continuous flow photoredox technology demonstrate the generality and practicality of this process.

The recently reported chemoselective reduction of phosphine oxides with 1,3-diphenyldisiloxane (DPDS) has opened up the possibility of additive-free phosphine oxide reductions in catalytic systems. Herein we disclose the use of this new reducing agent as an enabler of phosphorus redox recycling in Wittig, Staudinger, and alcohol substitution reactions. DPDS was successfully utilized in ambient-temperature additive-free redox recycling variants of the Wittig olefination, Appel halogenation, and Staudinger reduction. Triphenylphosphine-promoted catalytic recycling reactions were also facilitated by DPDS. Additive-free triphenylphosphine-promoted catalytic Staudinger reductions could even be performed at ambient temperature due to the rapid nature of phosphinimine reduction, for which we characterized kinetic and thermodynamic parameters. These results demonstrate the utility of DPDS as an excellent reducing agent for the development of phosphorus redox recycling reactions.

Aims & Objective:In this work, pyran derivatives were synthesized via a multicomponent reaction of ninhydrin, α-haloketones, dialkyl acetylenedicarboxylate, and triphenylphosphine in the presence of iron oxide magnetic nanoparticles (Fe3O4-MNPs) as efficient nanocatalyst in ethanol at room temperature.Materials & Methods:The biosynthesis of Fe3O4-MNPs was performed by Clover Leaf water extract. In addition, antioxidant activity was examined for the prepared compounds employing DPPH radical scavenging and ferric reduction activity potential (FRAP) experiment and comparing results with synthetic antioxidants (TBHQ and BHT).Results:Compound 5b showed excellent radical trapping activity and good reducing activity relative to standards (BHT and TBHQ).Conclusion:Some advantages of this procedure are: the workup of reaction is easy and the products can be separated easily by filtration. Fe3O4-MNPs display a good improvement in the yield of the product and showed significant reusable activity.

Organophosphorus compounds are used as drugs, pesticides, detergents, food additives, flame retardants, synthetic reagents, and catalysts, and their efficient synthesis is an important task in organic synthesis. To synthesize novel functional organophosphorus compounds, transition-metal-catalyzed methods have been developed, which were previously considered difficult because of the strong bonding that occurs between transition metals and phosphorus. Addition reactions of triphenylphosphine and sulfonic acids to unsaturated compounds in the presence of a rhodium or palladium catalyst lead to phosphonium salts, in direct contrast to the conventional synthesis involving substitution reactions of organohalogen compounds. Rhodium and palladium complexes catalyze the cleavage of P–P bonds in diphosphines and polyphosphines and can transfer organophosphorus groups to various organic compounds. Subsequent substitution and addition reactions proceed effectively, without using a base, to provide various novel organophosphorus compounds.1 Introduction2 Transition-Metal-Catalyzed Synthesis of Phosphonium Salts by Addition Reactions of Triphenylphosphine and Sulfonic Acids3 Rhodium-Catalyzed P–P Bond Cleavage and Exchange Reactions4 Transition-Metal-Catalyzed Substitution Reactions Using Diphosphines4.1 Reactions Involving Substitution of a Phosphorus Group by P–P Bond Cleavage4.2 Related Substitution Reactions of Organophosphorus Compounds4.3 Substitution Reactions of Acid Fluorides Involving P–P Bond Cleavage of Diphosphines5 Rhodium-Catalyzed P–P Bond Cleavage and Addition Reactions6 Rhodium-Catalyzed P–P Bond Cleavage and Insertion Reactions Using Polyphosphines7 Conclusions

A method was developed for the synthesis of dimethyl {2-[(arylmethylidene)amino]-2H-indazol-3-yl}malonates on the basis of a Knoevenagel condensation between 2-azidobenzaldehyde and dimethyl malonate, followed by treatment of the obtained adduct with aromatic aldehydes in the presence of polymer-supported triphenylphosphine. It was shown that the interaction of the synthesized Schiff bases with Corey ylide provided a route for the synthesis of 2-(aziridin-1-yl)indazoles.

Herein, we report the synthesis, characterization, and reactivity of the N-(isocyanoimine)triphenylphosphine (CNNPPh3) and bis(diisopropylamino)cyclopropenylidene (BAC) adducts of [Ce(NR2)3] (R = S...

The Wittig reaction between triphenylphosphine methylide and benzaldehyde has been studied both from conceptual and computational approaches. The supernucleophilic character of ylide accounts for the feasibility of the initial nucleophilic attack. The nature of bonding driving the formation of the first oxaphosphetane (OPA) intermediate in such a domino reaction is examined within a topological-based bonding evolution theory perspective. The sequence of the electronic flow associated to the changes in electron density supports a rationalization via two main electronic stages characterizing the single kinetic step: first, the C-C bond formation, which takes place via donation of electron density of the ylide carbon to the carbonyl carbon of benzaldehyde at a C-C distance of 2.02 Å, is formally associated to the transition state region; then, the P-O bond formation via the donation of electron density of the nonbonding region of the carbonyl oxygen to phosphorus at a P-O distance of 2.06 Å is located at the end of the reaction path. The detailed picture of bonding patterns suggests that the OPA formation in the Wittig mechanism can be better understood in terms of a

We wish to thank Lucite International for a studentship (P.L.) and EaStCHEM for support and access to the EaStCHEM Research Facility. We also thank Dr. H. Fruchtl for technical support. N.S. thanks the Univ. Grenoble Alpes, the CNRS and the ICMG FR 2607 for financial support. The Pcecic and Froggy platforms of the CIMENT infrastructure are also acknowledged (project “liqsim”).

Triphenylphosphine (TPP) surface-functionalized and F-108 Pluronic-stabilized gold nanoparticles (F-108@TPP-AuNPs) have been synthesized through a one-step approach, leading to well-defined (9.6±1.6 nm) and water-soluble nanoparticles by microwave heating an aqueous solution of TPP-AuI Cl in the presence of a Pluronic polymer under basic conditions. TPP release was negligible under physiological conditions, but enhanced significantly at an acidic pH (5.4) mimicking that of a cancer cell. Laser irradiation (532 nm) raised the temperature of an aqueous solution of F-108@TPP-AuNPs to 51.7 °C within 5 min, confirming efficient light-to-heat conversion capabilities without significant photodegradation. TEM confirmed intracellular localization of F-108@TPP-AuNPs in the cytosol, endosomes and lysosomes of HeLa cells. F-108@TPP-AuNPs were well tolerated by HeLa cells and zebrafish embryos at ambient temperatures and became toxic upon heat activation, suggesting synergistic interactions between heat and cytotoxic action by TPP.

A novel and efficient method has been proposed for the synthesis of 1,4-benzodiazepine-5-ones from o-nitrobenzoic N-allylamides by using molybdenyl acetylacetonate and copper(II) trifluoromethanesulfonate as catalysts in the presence of triphenylphosphine. This synthesis process involves nitrene formation, C–H bond insertion, C=C bond rearrangement, and C–N bond formation cascade reactions via copper- and molybdenum-catalyzed mediation. The method features a wide substrate scope and a moderate to high yield (up to 90%), exhibiting the possibility for practical applications.