OMe Groups Research Articles

Luminescent cyclometalated alkynylplatinum(II) complexes with 1,3-di(pyrimidin-2-yl)benzene ligands: synthesis, electrochemistry, photophysics and computational studies.

In this article, we report on a series of cyclometalated chloro- and alkynyl-platinum(II) complexes bearing various tridentate N^C^N-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene. The X-ray crystal structures of two alkynyl-platinum(II) complexes were determined and other structures were DFT-calculated. Electrochemical and DFT-computational studies suggest a ligand-centred reduction on the R1-substituted N^C^N ligand, whereas oxidation likely occurs either on the Pt-phenylacetylide moiety and/or the cyclometalated ligand. In CH2Cl2 solution at room temperature, the complexes show phosphorescent emissions ranging from green to orange, depending on the R1 and R2 substituents on the ligands. In KBr solid state matrix, excluding complexes bearing a trifluoromethyl substituted ligand, all compounds exhibit red emission. The presence of an alkynyl ancillary ligand has limited influence on absorption and emission spectra except in the case of the complex with the strongly electron-donating diphenylamino R2 substituent on the alkynyl ligand, for which a significant red-shift was observed. The alkynyl Pt(II) complex with OMe groups as both R1 and R2 substituents shows the best emission quantum yield (0.81 in CH2Cl2 solution) in this series. The full series of DFT calculated band gaps correlated generally well with the electrochemical and absorption data and reasonably model the impact of the substituents on the electronics of these complexes.

Controlling rotary motion of molecular motors based on oxindole.

Molecular motors are essential components of artificial molecular machines, which can be used to manipulate and amplify mechanical motion at the nanoscale to create machine-like function. Since the discovery of light-driven rotary molecular motors, the field has been widely developed, including the introduction of molecular motors based on oxindole by our group in 2019. The rotational properties of molecular motors, e.g. absorption wavelength, quantum yield and rotation speed, often critically depend on substituent effects. Up to now, the substituent effects of oxindole-based molecular motors have not yet been investigated. Herein, we present a family of oxindole-based molecular motors functionalised at three different positions on the motor core, with either CN or OMe groups. The motors prepared in this work retain the favourable features of oxindole-based motors, i.e. simple synthesis and visible light addressability. We find that functionalisation has substantial effects on the absorption wavelength of the motors, meanwhile the rotation speed is unaffected. Furthermore, we found that functionalisation of the oxindole molecular motors increases their quantum efficiency considerably in comparison to previous motors of their class.

Chromosome numbers and heterochromatin variation in introgressed and non-introgressed populations ofEpidendrum(Orchidaceae: Epidendroideae): interspecific transfers of heterochromatin lead to divergent variable karyotypes in the parental populations

AbstractSome groups in Epidendrum have stable chromosome numbers, whereas the species of Epidendrum subgenus Amphiglottium exhibit high levels of chromosome number variability and other genomic alterations. Polyploidy and dysploidy have both been invoked to explain chromosome number variation in the subgenus, but little is known about what is driving the high frequency of chromosome modification within some species in this group. To test whether hybridization and introgression are involved, we use fluorochrome staining to evaluate the chromosome numbers and heterochromatin bands in E. subgenus Amphiglottium, including individual parental genotypes from introgressed and non-introgressed populations. Two main types of heterochromatin were observed forming CMA and DAPI bands in Epidendrum spp. B chromosomes were identified in some individuals. In non-introgressed populations, E. secundum has three cytotypes, 2n = 28, 56 and 84, found in different parts of its geographical range and a small number of DAPI bands. In introgressed populations of E. secundum, there was dysploid variation among individuals that were morphologically typical parental plants, and in one introgressed population a high number of DAPI bands was observed in what appeared on morphological grounds to be pure parental individuals. Our data corroborate the hypothesis that hybridization and introgression play a role in generating chromosome variation (number and form) and heterochromatin diversification in E. subgenus Amphiglottium.

Oligonucleotides containing 2′-O-methyl-5-(1-phenyl-1,2,3-triazol-4-yl)uridines demonstrate increased affinity for RNA and induce exon-skipping in vitro

The nucleotide monomer containing the 1-phenyl-1,2,3-triazole group attached to the 5-position of 2′-O-methyluridine is hereby presented together with a derivative further substituted with a p-sulfonamide group on the phenyl ring. Both were conveniently synthesised, and synergistic effect of the modifications were demonstrated when introduced into oligonucleotides and hybridised to complementary RNA. The combination of stacking of the phenyltriazoles and the conformational steering from the 2′-OMe group gave thermally very stable duplexes. Exon skipping in the distrophin transcript using 20-mer 2′-OMePS sequences with two phenyltriazoles introduced in different positions with and without the sulfonamide demonstrated efficient exon skipping but at the same level as the 2′-OMePS reference ASO.

Theoretical study of gas-phase detoxication of DMMP and DMPT using ammonia-borane and its analogous compound

The detoxication of DMMP (Dimethyl methylphosphonate) and DMPT (O, S-dimethyl methylphosphonothiolate) via hydrogenation have been investigated computationally employing density functional theory (DFT). In this present study, we aim to explore the direct molecular H2 assisted as well as ammonia-borane (NH3BH3) and 3-methyl-1,2-BN-cyclopentane (denoted as cy-AB) assisted hydrogenation pathways of DMMP and DMPT in order to detoxify them. The detoxication of DMMP has been carried out by successive elimination of two -OMe groups. However, in the case of DMPT, two possibilities have been identified because of two different substituents, -OMe and -SMe. In possibility-I, the elimination of the -OMe group occurs at the beginning, followed by the -SMe group, whereas in possibility-II, the reverse order of elimination occurs for -OMe and -SMe groups. During the detoxication of DMMP using both NH3BH3 and cy-AB as the assisting reagents, the first step has been identified as the rate-determining step (RDS) in which the hydrogens attached to the N- and B-centers of NH3BH3 are transferred to the O-center of PO and P-center, respectively. In harmony with DMMP detoxication, for DMPT also, analyzing the activation barriers, it can be articulated that for both NH3BH3 and cy-AB assisted pathways, both the possibilities are equally feasible as in both the possibilities the common first step is the RDS. Therefore, our computational study is designed to explore the assisting efficiency of NH3BH3 and its cyclic analogue for detoxifying the OPCs.

Photochemical studies of new synthetic derivatives of avobenzone under sunlight using UV-spectroscopy

Avobenzone is the most widely used chemical UV-A filter in sunscreen formulations and is prone to photodegradation under UV radiations/sunlight. Various methods have been employed to improve the photostability of avobenzone using triplet quenchers, antioxidants, and micelles. The current report has adopted a skeletal modification approach to improving the photostability of avobenzone. Electron-donating –OMe group has been replaced with electron-withdrawing –COOH/–COOMe group to yield the new derivatives, namely, avobenzone-acid/avobenzone-ester. New avobenzone derivatives were chemically synthesized and characterized using UV-spectroscopy which confirmed that they retained broad-spectrum UV-A filtering activity with additional UV-C filtering activity. Interestingly, the keto-form was present in crystals and 94:6 ratio of enol-: keto-forms were present in aprotic DMSO solvent confirming the occurrence of keto-enol tautomerization in avobenzone-acid. The photochemical properties of the new derivatives such as photostability, recovery from photodegraded enol forms in dark, and the effect of photostabilizer glutathione were accessed under sunlight using UV-spectroscopy. These studies indicate that the new derivatives compared to naïve avobenzone have improved photostability, rapid recovery from degradation products in the dark in DMSO, and enhanced response to photostabilizer glutathione. Computationally, Bond Dissociation Energy (BDE) and influence of DMSO solvent on the energetics of keto-enol tautomerizations of avobenzone and the new derivatives were calculated using density functional theory (DFT). These calculations support the experimental observations of the improved photochemical properties of the new avobenzone derivatives with retention of broad-spectrum UV-A absorbance activity. The current report has demonstrated that the skeletal modification approach has improved the intrinsic photostability of avobenzone and the new avobenzone derivatives may serve as a potential alternative to avobenzone in sunscreen lotions.

Pendent Relay Enhances H2O2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co-N2O2 Complexes.

Generally, cobalt-N2O2 complexes show selectivity for hydrogen peroxide during electrochemical dioxygen (O2) reduction. We recently reported a Co(III)-N2O2 complex with a 2,2'-bipyridine-based ligand backbone which showed alternative selectivity: H2O was observed as the primary reduction product from O2 (71 ± 5%) with decamethylferrocene as a chemical reductant and acetic acid as a proton donor in methanol solution. We hypothesized that the key selectivity difference in this case arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(III)-hydroperoxide species. To interrogate this hypothesis, we have prepared a new Co(III) compound that contains pendent -OMe groups poised to direct protonation toward the proximal O atom of this hydroperoxo intermediate. Mechanistic studies in acetonitrile (MeCN) solution reveal two regimes are possible in the catalytic response, dependent on added acid strength and the presence of the pendent proton donor relay. In the presence of stronger acids, the activity of the complex containing pendent relays becomes O2 dependent, implying a shift to Co(III)-superoxide protonation as the rate-determining step. Interestingly, the inclusion of the relay results in primarily H2O2 production in MeCN, despite minimal difference between the standard reduction potentials of the three complexes tested. EPR spectroscopic studies indicate the formation of Co(III)-superoxide species in the presence of exogenous base, with greater O2 reactivity observed in the presence of the pendent -OMe groups.

Highly active electrocatalytic CO2 reduction with manganese N-heterocyclic carbene pincer by para electronic tuning

Electronic tuning by para substitutions was explored to achieve a highly active manganese N-heterocyclic carbene pincer complex for the selective electrocatalytic reduction of CO2 to CO. [MnCNCOMe]BF4 (L2-Mn) bearing an electron-donating group (–OMe) showed high activity with 63 × catalytic current enhancement, average Faradaic efficiency of 104%, and a TOFmax value of 26,127 s−1, which is 127 times higher than that of unsubstituted [MnCNCH]Br (L1-Mn) reported previously. In contrast, the electron-withdrawing group (–COOMe) in [MnCNCCOOMe]PF6 (L3-Mn) inhibited the electrocatalytic activity. Ambient Brønstic acid, however, suppressed the activity of L2-Mn probably due to the protonation of the –OMe group. These findings indicate a potential electronic tuning strategy to improved manganese N-heterocyclic carbene catalysts for CO2 reduction.

Semi-synthesis of novel buprenorphine derivatives and their anti-nociceptive properties and dependency potential

Novel 1,2,3-triazole-tethered N-norbuprenorphine derivatives with an OMe or OH group at the C3 position were synthesized alongside with evaluation of their analgesic properties. The analgesic activities of the resulting library were investigated via tail flick test in mice. Our results indicated that 10b and 10e were as effective as the starting compounds 8 and 9 with ED50 equal to 16.59 and 19.44 mg/kg, respectively. To investigate the effect of a methyl group at C3 on biological properties, the most active compounds were O-demethylated and their anti-nociceptive effects were assessed. The new O-demethylated derivatives (11b and 11e) showed better analgesic properties than the parent compounds with ED50 of 14.73 and 15.80 mg/kg, respectively. Naloxone prevented the analgesic effect of the synthesized compounds, indicating that the opioid receptors are highly involved in the anti-nociceptive effects. The potential dependency effects of the most potent derivatives were studied by condition place preference test in mice and compared with morphine and buprenorphine. Interestingly, 10b, 10e, 11b, and 11e did not show any dependency effect, similar to buprenorphine.

Effect of γ-secretase inhibitor on middle ear ultrastructures in ovalbumin-mediated otitis media with effusion in rats

Objective: To study the effect of the inhibitor of Notch signaling pathway-γ-secretase inhibitor DAPT on the ultrastructures of middle ear in the ovalbumin (OVA)-mediated allergic OME in vivo. Methods: Male Sprague-Dawley (SD) rats, weighing 250-300 g, were completely and randomly divided into three groups (5 rats, 10 ears in each group):(1)Control group(2)OME group(3)OME+DAPT group. Rats in the OME group underwent systemic and local sensitization by intraperitoneal and intratympanic injection of ovalbumin to make the model of OVA-induced OME. Rats in the control group were sensitized with PBS. On the basis of establishing the OME model, OME+DAPT group were intraperitoneal injected with DAPT (10 mg/kg) for seven consecutive days and were administered before intratympanic injection of ovalbumin. After the model was successfully established, endoscopy,H&E staining and scanning electron microscopy were used to study the histology and mucous-ciliary ultrastructures of the non-ciliated and ciliated mucosa in the middle ear of each group. One-way ANOVA and Tukey methods were used for statistical analysis. Results: H&E staining showed that the three groups had statistically significant differences in submucosal thickness both in non-ciliated and ciliated regions (non-ciliated area:(6.83±1.47)μm, (38.58±9.57)μm, (32.17±11.89)μm, respectively. F=107.9;cilia area:(26.69±3.22)μm, (30.41±6.75)μm, (26.76±4.06)μm, respectively. F=5.62,both P<0.01). The thickness of the submucosa in the non-ciliated area and the cilia area of the OME group were significantly thicker than that of control group (F=42.08 and 4.40,both P<0.05); the thickness of the non-ciliated area and the ciliated area in OME+DAPT group were reduced compared to OME group(F=1.55 and 2.77,both P<0.05). Scanning electron microscopy showed that the array of cilia on the middle ear mucosa was disorderly arranged and inversed, this phenomenon was relieved in the OME+DAPT group. The number of goblet cells in the control group, OME group, and OME+DAPT group were 9.87±1.92; 15.67±5.77; 10.33±1.99 respectively and the difference between them was statistically significant (F=11.43, P<0.01). The number of goblet cells in the OME group were significantly higher than those in the control group (F=9.00,P<0.01) and the number of goblet cells in the OME+DAPT group were decreased compared to those of OME group (F=8.41, P<0.01). Conclusions: The study demonstrates the pathological changes of the ultrastructure in middle ear in OVA-induced OME and the effect of the γ-secretase inhibitor on it. In OME group, the cilia are disorderly arranged and inversed, the number of goblet cell is increased and they are swelled which suggest the hypersecretion of the mucus. DAPT can regulate OVA-induced allergic inflammation and relieve pathological changes of ultrastructure in middle ear mucociliary transport system through alleviating submucosal inflammation, reducing the hypersecretion of goblet cell and the morphological damage of cilia through the Notch signaling pathway.

Cobalt‐Catalyzed C—H Allylation of Arenes with Allylic Amines

Main observation and conclusion[Cp*Co(CO)I2] effectively catalyzes pyridyl‐directed C—H allylation of arenes with allylic amines in the presence of AgOAc and CF3COOAg. The reaction features ortho‐position monoallylation of 2‐pyridylarenes, giving the allylated arenes in moderate to high yields. A range of functional groups including OMe, Me, Ph, F, Cl, Br, CF3, C(O)Me, COOEt, and COOH groups are tolerated. Pyrimidyl‐directed C—H allylation of arenes were also performed under the same conditions. Reaction of 2‐phenylpyrimidine, 2‐(4‐methoxyphenyl)pyrimidine, and 2‐(3‐fluorophenyl)pyrimidine leads to a mixture of ortho‐position mono‐ and bisallylation products. Reaction of other 2‐(substituted aryl)pyrimidines resulted in ortho‐position monoallylation products.

Synthesis of Acridinium Photocatalysts via Site-Selective C–H Alkylation

Acridinium dyes have been broadly used as photocatalysts, but it remains synthetically challenging to fine-tune their catalytic performance by functionalization of their structural cores. Acridiniu...

In Silico and Biological Evaluation of N‐(2‐methoxyphenyl) Substituted Pyrazoles Accessed via a Sonochemical Method

AbstractIn view of remarkable biological properties including anticancer activities of N‐aryl pyrazoles we have explored N‐(2‐methoxyphenyl) substituted pyrazoles and related derivatives as potential cytotoxic agents. In silico methods were adopted to understand/predict the biochemical and physiological effects, toxicity, and biological profiles of these compounds thereby assessing the potential drug‐likeness of the hit molecule. The target compounds were conveniently prepared via a sonochemical method involving the C−N bond forming reactions in the presence of CuI in DMSO. A library of N‐aryl pyrazole derivatives were synthesized via coupling of iodoarenes with pyrazole whereas the use of other N‐heteroarene such as imidazole and pyrrole in place of pyrazole afforded the corresponding product. The in vitro evaluation of all these compounds was carried out against MDAMB‐231 and MCF‐7 cell lines and subsequently against SIRT1. The pyrazole derivative 3 c showed encouraging growth inhibition of both MDAMB‐231 and MCF‐7 cell lines (59 and 48 % at 10 μM, respectively) and inhibition of SIRT1 (IC50 ∼ 6.21±0.42 μM) in vitro. The molecular docking studies suggested H‐bonding (involving OMe group), Van der Waals and hydrophobic interactions of 3 c with important amino acid residues in the catalytic domain of SIRT1. Overall, cell‐based as well as enzyme assay, molecular modelling, in silico ADME/TOX prediction and in vitro stability studies suggested 3 c as a potential hit molecule.

Widening the Window of Spin-Crossover Temperatures in Bis(formazanate)iron(II) Complexes via Steric and Noncovalent Interactions

Bis(formazanate)iron(II) complexes undergo a thermally induced S = 0 to S = 2 spin transition in solution. Here we present a study of how steric effects and π-stacking interactions between the triarylformazanate ligands affect the spin-crossover behavior, in addition to electronic substituent effects. Moreover, the effect of increasing the denticity of the formazanate ligands is explored by including additional OMe donors in the ligand (7). In total, six new compounds (2–7) have been synthesized and characterized, both in solution and in the solid state, via spectroscopic, magnetic, and structural analyses. The series spans a broad range of spin-crossover temperatures (T1/2) for the LS ⇌ HS equilibrium in solution, with the exception of compound 6 which remains high-spin (S = 2) down to 210 K. In the solid state, 6 was shown to exist in two distinct forms: a tetrahedral high-spin complex (6a, S = 2) and a rare square-planar structure with an intermediate-spin state (6b, S = 1). SQUID measurements, 57Fe Mössbauer spectroscopy, and differential scanning calorimetry indicate that in the solid state the square-planar form 6b undergoes an incomplete spin-change-coupled isomerization to tetrahedral 6a. The complex that contains additional OMe donors (7) results in a six-coordinate (NNO)2Fe coordination geometry, which shifts the spin-crossover to significantly higher temperatures (T1/2 = 444 K). The available experimental and computational data for 7 suggest that the Fe···OMe interaction is retained upon spin-crossover. Despite the difference in coordination environment, the weak OMe donors do not significantly alter the electronic structure or ligand-field splitting, and the occurrence of spin-crossover (similar to the compounds lacking the OMe groups) originates from a large degree of metal–ligand π-covalency.

P-Nitroterphenyl units for near-infrared two-photon uncaging of calcium ions

Near-infrared two-photon (NIR-2P) uncaging reactions are useful for precise investigations of the roles of biologically active compounds in various phenomena. In this study, we synthesized new NIR-2P-responsive chromophores with terphenyl backbones featuring an ethylene glycol tetraacetic acid (EGTA) unit as a Ca2+-selective chelator. The photolabile Ca2+ chelators were synthesized in high yields (83 % for 1a, 45 % for 1b) from commercially available starting materials. One- and two-photon photochemical excitations of the synthesized terphenyl derivatives featuring two different electron-donating groups (dimethylamino (NMe2) and methoxyl (OMe)), which were thermally stable at least 36 h at 37 C in HEPES buffer (pH 7.4), were conducted to clarify the substituent effect on the photophysical and photochemical properties. The NMe2 group, which is a stronger electron-donating group, has led to a higher two-photon cross-section (σ2 = 75 GM at 780 nm) compared to the OMe group (σ2 = 9 GM at 720 nm) in a pH = 7.4 HEPES buffer solution, although the molar extinction coefficient (ε) of the NMe2-substituted one (ε = 10,371 at λmax =363 nm) was lower than that of the OMe-derivative (ε = 14,351 at λmax = 344 nm). The quantum yield (Φ = 0.04) for the decomposition of the NMe2-substituted caged compound was lower than that for the OMe-substituted caged compound (Φ = 0.40). One and two-photon uncaging efficiency values of the OMe substituted compound, ε × Φ = 5740 and σ2 × Φ = 3.6, were higher than those of the NMe2-substituted compound, 415 and 3.0, respectively. Laser flash photolysis experiments clarified the decay rate constants (2.5 × 106 and 1.1 × 102 s−1) of aci-nitro intermediates formed during the uncaging process. A concentration jump of Ca2+ was confirmed in the photolysis of caged calcium compounds newly synthesized in this study, indicating the terphenyl derivatives can be also utilized in physiological experiments. The corresponding acetoxymethyl esters were also prepared for physiological studies.

Photonic materials derived from the [closo-B10H10]2−anion: tuning photophysical properties in [closo-B10H8-1-X-10-(4-Y-NC5H5)]−

Substitution of the parent [closo-B10H9-1-NC5H5]−either at the B(10) position or at the pyridine ring tunes absorption and emission energy.

Recent advances in understanding oligonucleotide aptamers and their applications as therapeutic agents.

The innovative discovery of aptamers was based on target-specific treatment in clinical diagnostics and therapeutics. Aptamers are synthetic, single-stranded oligonucleotides, simply described as chemical antibodies, which can bind to diverse targets with high specificity and affinity. Aptamers are synthesized by the SELEX technique, and possess distinctive properties as small size (10-50kDa), higher stability, easy manufacture and less immunogenicity. These oligonucleotides are easily degraded by nucleases, so require some important modifications like capping and incorporation of modified nucleotides. RNA aptamers can be modified chemically on 2' positions using -NH3, -F, -deoxy, or -OMe groups to enhance their nuclease resistance. Aptamers have been employed for multiple purposes, as direct drugs or aptamer-drug conjugates targeted against different diseased cells. Different aptamer-conjugated nanovehicles (e.g., micelles, liposomes, silica nano-shells) have been designed to transport diverse anticancer-drugs like doxorubicin and cisplatin in bulk to minimize systemic cytotoxicity. Some drug-loaded nanovehicles (up to 97% loading capacity) and conjugated with specific aptamer resulted in more than 60% tumor inhibition as compared to unconjugated drug-loaded nanovehicles which showed only 31% cancer inhibition. In addition, aptamers have been widely used in basic research, food safety, environmental monitoring, clinical diagnostics and therapeutics. Different FDA-approved RNA and DNA aptamers are now available in the market, used for the treatment of diverse diseases, especially cancer. These aptamers include Macugen, Pegaptanib, etc. Despite a good progress in aptamer use, the present-day chemotherapeutics and drug targeting systems still face great challenges. Here in this review article, we are discussing nucleic acid aptamers, preparation, role in the transportation of different nanoparticle vehicles and their applications as therapeutic agents.

Tackling Educational Inequalities with Social Psychology: Identities, Contexts, and Interventions

AbstractSome groups of students—typically those who have suffered because of historical inequality in society—disproportionately experience psychological barriers to educational success. These psychological barriers—feelings of threat to their social identity and the sense that their identity is incompatible with educational success—make substantial contributions to inequalities in educational outcomes between groups, even beyond economic, historical, and structural inequalities. A range of wise psychological interventions can help remove these barriers by targeting students’ subjective interpretation of their local educational context. In this review, we outline the Identities in Context model of educational inequalities, which proposes that interactions between students’ social identities and features of the local educational context—expectations about a group's academic performance, a group's representation in positions associated with academic success, and a group's orientation towards education—can trigger social identity threat and identity incompatibility in ways that vary considerably across contexts. We present an implementation process, based on the Identities in Context model, that academic researchers, policymakers, and practitioners can follow to help them choose and tailor wise interventions that are effective in reducing educational inequalities in their local context. Throughout the review, we make policy recommendations regarding how educational practices can be altered to help remove psychological barriers for underperforming groups of students and so reduce educational inequalities.

Naphthalimide-based macrophage nucleus imaging probes

The photophysical properties of naphthalimide-based fluorophores can be easily tuned by chemical manipulation of the substituents on that privileged scaffold. Replacement of a OMe group at position 6 in 2-(hydroxyl)ethyl-naphthalimide derivatives by diverse amines, including 2-(hydroxyl)ethylamine, trans-(4-acetamido)cyclohexylamine and azetidine increases the solvatochromic (ICT) character, while this replacement in 2-(dimethylamino)ethyl-naphthalimide analogues (PET fluorophores) decrease their solvent polarity sensitivity or even reversed them to solvatochromic fluorophores. These fluorophores resulted macrophage nucleus imaging probes, which bind DNA as intercalants and showed low cytotoxicity in human cancer cells.

Methoxylation of Acyl Fluorides with Tris(2,4,6-trimethoxyphenyl)phosphine via C-OMe Bond Cleavage under Metal-Free Conditions.

Acyl fluorides are subjected to methoxylation with tris(2,4,6-trimethoxyphenyl)phosphine (TMPP) to afford the corresponding methyl esters in good to excellent yields. This transformation is featured by C(sp2)-OMe bond cleavage under metal-free conditions. Unprecedented utilization of TMPP as a methoxylating agent realized the installation of an OMe group into the desired products.