Prognostic impact of concomitant pH-regulating drugs in patients with non-small cell lung cancer receiving epidermal growth factor receptor tyrosine kinase inhibitors: the Tokushukai REAl-world Data project 01-S1.

Purpose: This study aimed to examine the prognostic impact of concomitant pH-regulating drug use in patients with epidermal growth factor receptor (EGFR)-mutation-positive non-small-cell lung cancer (NSCLC) receiving EGFR-tyrosine kinase inhibitors (TKIs).

Methods: We conducted a nationwide retrospective cohort study and reviewed clinical data of consecutive patients with NSCLC treated with the first-line EGFR-TKIs in 46 hospitals between April 2010 and March 2020. Cox regression analyses were conducted to examine the differences in overall survival (OS) between patients treated with and without concomitant pH-regulating drugs, including potassium-competitive acid blockers (P-CABs), proton pump inhibitors (PPIs), and H-receptor antagonists (HRAs).

Nickel-Catalyzed Ring-Opening C-O Functionalization of -Xanthenoxanthenes for 8-Substituted Binaphthol Synthesis.

Herein, we disclose the Ni-catalyzed ring-opening C-O functionalization of -xanthenoxanthenes using Grignard reagents that forms 8-monofunctionalized binaphthols. 1,2-Bis(dicyclohexylphosphino)ethane was the best ligand for alkylations and ICy for arylation. After mechanistic investigations, we assumed that the reaction proceeds via C-O reduction and subsequent C-O functionalization.

Ni-Catalyzed α-Selective C-H Borylations of Naphthalene-Based Aromatic Compounds.

The ability of α-borylated naphthalene-based aromatic compounds is important because it provides ready access to interesting novel extended π-systems. In this report, we disclose the Ni-catalyzed α-selective C-H borylations of naphthalene-based aromatic compounds. The reaction proceeds with -xanthenoxanthene and other aromatic compounds to regioselectively afford the α-borylated products without directing groups.

C-H Triflation of BINOL Derivatives Using DIH and TfOH.

C-H trifluoromethanesulfonyloxylation (triflation) of 1,1'-bi-2-naphthol (BINOL) derivatives has been established under mild conditions using 1,3-diiodo-5,5-dimethylhydantoin (DIH) and trifluoromethanesulfonic acid (TfOH). Up to eight TfO groups can be introduced in a single operation. The resulting highly oxidized BINOL derivatives can be successfully converted to 8,8'-dihydroxy BINOL and bisnaphthoquinone compounds.

Cu-Catalyzed Aerobic Oxidative C-H/C-O Cyclization of 2,2'-Binaphthols: Practical Synthesis of PXX Derivatives.

Cu-catalyzed C-H/C-O cyclization of 2,2'-binaphthol, using air as an oxidant, was developed. C-H functionalization of binaphthols occurred at the 8,8'-position to form peri-xanthenoxanthenes that exhibit high charge-carrier mobility. The reaction can tolerate a wide variety of functional groups and afforded the corresponding peri-xanthenoxanthene derivatives via an efficient procedure.

Amine/Hydrido Bifunctional Nanoporous Silica with Small Metal Nanoparticles Made Onsite: Efficient Dehydrogenation Catalyst.

Multifunctional catalysts are of great interest in catalysis because their multiple types of catalytic or functional groups can cooperatively promote catalytic transformations better than their constituents do individually. Herein we report a new synthetic route involving the surface functionalization of nanoporous silica with a rationally designed and synthesized dihydrosilane (3-aminopropylmethylsilane) that leads to the introduction of catalytically active grafted organoamine as well as single metal atoms and ultrasmall Pd or Ag-doped Pd nanoparticles via on-site reduction of metal ions. The resulting nanomaterials serve as highly effective bifunctional dehydrogenative catalysts for generation of H from formic acid.

Grafted Polymethylhydrosiloxane on Hierarchically Porous Silica Monoliths: A New Path to Monolith-Supported Palladium Nanoparticles for Continuous Flow Catalysis Applications.

Polymethylhydrosiloxane has been grafted on the surface of a hierarchically porous silica monolith using a facile catalytic reaction between Si-H and silanol to anchor the polymer. This easy methodology leads to the functionalization of the surface of a silica monolith, where a large amount of free Si-H bonds remain available for reducing metal ions in solution. Palladium nanoparticles of 15 nm have been synthesized homogeneously inside the mesopores of the monolith without any stabilizers, using a flow of a solution containing Pd.

Surface functionalization of silica by Si-H activation of hydrosilanes.

Inspired by homogeneous borane catalysts that promote Si-H bond activation, we herein describe an innovative method for surface modification of silica using hydrosilanes as the modification precursor and tris(pentafluorophenyl)borane (B(C6F5)3) as the catalyst. Since the surface modification reaction between surface silanol and hydrosilane is dehydrogenative, progress and termination of the reaction can easily be confirmed by the naked eye. This new metal-free process can be performed at room temperature and requires less than 5 min to complete.

Recyclable functionalization of silica with alcohols via dehydrogenative addition on hydrogen silsesquioxane.

Synthesis of class II hybrid silica materials requires the formation of covalent linkage between organic moieties and inorganic frameworks. The requirement that organosilylating agents be present to provide the organic part limits the synthesis of functional inorganic oxides, however, due to the water sensitivity and challenges concerning purification of the silylating agents. Synthesis of hybrid materials with stable molecules such as simple alcohols, rather than with these difficult silylating agents, may therefore provide a path to unprecedented functionality.

Enhanced fluorescence detection of metal ions using light-harvesting mesoporous organosilica.

Enhanced fluorescence detection of metal ions was realized in a system consisting of a fluorescent 2,2'-bipyridine (BPy) receptor and light-harvesting periodic mesoporous organosilica (PMO). The fluorescent BPy receptor with two silyl groups was synthesized and covalently attached to the pore walls of biphenyl (Bp)-bridged PMO powder. The fluorescence intensity from the BPy receptor was significantly enhanced by the light-harvesting property of Bp-PMO, that is, the energy funneling into the BPy receptor from a large number of Bp groups in the PMO framework which absorbed UV light effectively.

Synthesis of a spirobifluorene-bridged allylsilane precursor for periodic mesoporous organosilica.

A novel spirobifluorene-bridged allylsilane precursor, which can be easily purified by silica gel chromatography, was prepared by using a new molecular building block for allylsilane sol-gel precursors (MBAS) and successfully converted into a highly fluorescent periodic mesoporous organosilica film.

Mesostructured organosilica with a 9-mesityl-10-methylacridinium bridging unit: photoinduced charge separation in the organosilica framework.

Polycondensation of 9-mesityl-10-methylacridinium-bridged organosilane in the presence of a nonionic surfactant yielded a mesostructured organosilica solid with a functional framework that exhibited long-lived photoinduced charge separation.

Theoretical studies on Si-C bond cleavage in organosilane precursors during polycondensation to organosilica hybrids.

Molecular orbital theory calculations were carried out to predict the occurrence of Si-C bond cleavage in various organosilane precursors during polycondensation to organosilica hybrids under acidic and basic conditions. On the basis of proposed mechanisms for cleavage of the Si-C bonds, the proton affinity (PA) of the carbon atom at the ipso-position and the PA of the carbanion generated after Si-C cleavage were chosen as indices for Si-C bond stability under acidic and basic conditions, respectively. The indices were calculated using a density functional theory (DFT) method for model compounds of organosilane precursors (R-Si(OH)(3)) having organic groups (R) of benzene (Ph), biphenyl (Bp), terphenyl (Tph), naphthalene (Nph), N-methylcarbazole (MCz), and anthracene (Ant).

Visible-light-harvesting periodic mesoporous organosilica.

Highly ordered periodic mesoporous organosilica synthesized from a newly designed 9(10H)-acridone bridged organosilane precursor exhibited efficient light-harvesting antenna properties for visible light, at wavelengths up to 450 nm.

Fluorescence emission from 2,6-naphthylene-bridged mesoporous organosilicas with an amorphous or crystal-like framework.

We report that 2,6-naphthylene-bridged periodic mesoporous organosilicas exhibit unique fluorescence behavior that reflects molecular-scale periodicities in the framework. Periodic mesoporous organosilicas consisting of naphthalene-silica hybrid frameworks were synthesized by hydrolysis and condensation of a naphthalene-derived organosilane precursor in the presence of a template surfactant. The morphologies and meso- and molecular-scale periodicities of the organosilica materials strongly depend on the synthetic conditions.

Direct synthesis of porous organosilicas containing chiral organic groups within their framework and a new analytical method for enantiomeric purity of organosilicas.

Organosilica porous solids containing chiral organic moieties in the framework with an enantiomeric purity of 95% ee, estimated by eluting organic constituent units from chiral organosilicas, were synthesized from a newly designed chiral (R)-(+)-1,2-bis(trimethoxysilyl)phenylethane precursor via a surfactant-mediated self-assembly approach.

Rhodium-catalyzed asymmetric synthesis of indanones: development of a new "axially chiral" bisphosphine ligand.

A rhodium-catalyzed asymmetric isomerization of racemic alpha-arylpropargyl alcohols to beta-chiral indanones has been developed. High enantioselectivity has been realized by the use of a newly developed axially chiral bisphosphine ligand. This ligand is unique in the sense that its axial chirality is fixed to a single configuration upon complexation to a transition metal due to other chiral axes existing within the same molecule.

Facile preparation of a new BINAP-based building block, 5,5'-diiodoBINAP, and its synthetic application.

[reaction: see text] Bis(pyridine)iodonium tetrafluoroborate was successfully used for regioselective iodination of BINAP dioxide to give 5,5'-diiodoBINAP dioxide in an excellent yield of 92%, with no observed formation of 4,4'-diiodoBINAP dioxide. A Sonogashira cross-coupling reaction with 5,5'-diiodoBINAP dioxide gave the desired bis(trimethylsilylethynyl) product in 86% yield. The resulting 5,5'-disubstituted BINAP dioxides were reduced to the corresponding phosphines, which were used as chiral ligands for rhodium-catalyzed asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone to give 3-phenylcyclohexanone in excellent yield with high enantioselectivity.

A new synthetic route to enantiomerically pure axially chiral 2,2'-bipyridine N,N'-dioxides. Highly efficient catalysts for asymmetric allylation of aldehydes with allyl(trichloro)silanes.

New axially chiral 2,2'-bipyridine N,N'-dioxides 1 were obtained in an enantiomerically pure form by way of cyclic diesters 6 or 7 which were formed by the esterification of diols 2 with (R)-2,2'-bis(chlorocarbonyl)-1,1'-binaphthalene (5). Epimerization of the kinetic products at the ester formation (R(nap),S(pyr))-6 to the thermodynamically stable isomers (R(nap),R(pyr))-7 was observed in refluxing toluene or in the presence of trifluoroacetic acid. One of the N,N'-dioxides 1a which is substituted with phenyl groups at the 6 and 6' positions was found to be highly catalytically active and enantioselective for the asymmetric allylation of aldehydes with allyl(trichloro)silane giving homoallyl alcohols.

Functionalization on silica gel with allylsilanes. A new method of covalent attachment of organic functional groups on silica gel.

Treatment of an (allyl)organosilane with silica gel in refluxing toluene brought about deallylation forming an Si-O-Si bond with the silicon on the silica gel. This Si-O-Si bond formation provides us with a new reliable method for the functionalization of a silica gel surface.

Nickel-catalyzed asymmetric grignard cross-coupling of dinaphthothiophene giving axially chiral 1,1'-binaphthyls.

Asymmetric cross-coupling of dinaphtho[2,1-b:1',2'-d]thiophene with ArMgBr (Ar = Ph, 4-MeC6H4, 4-MeOC6H4) proceeded with high enantioselectivity in THF at 20 degrees C in the presence of 3 mol % of a nickel catalyst generated from Ni(cod)2 and a chiral oxazoline-phosphine ligand to give high yields of axially chiral 2-mercapto-2'-aryl-1,1'-binaphthyls, whose enantiomeric excesses are over 93%. The mercapto group in the chiral binaphthyl was converted into iodo, boryl, and phosphino groups without racemization.

A novel axially chiral 2,2'-bipyridine N,N'-dioxide. Its preparation and use for asymmetric allylation of aldehydes with allyl(trichloro)silane as a highly efficient catalyst.

[reaction: see text] New axially chiral 2,2'-bipyridine N,N'-dioxides were obtained by a new method that does not involve any procedures for the separation of enantiomers. One of the dioxides, (R)-3,3'-bis(hydroxymethyl)-6,6'-diphenyl-2,2'-bipyridine N,N'-dioxide, exhibited extremely high catalytic activity for the asymmetric allylation of aldehydes with allyl(trichloro)silane. The allylation of aromatic aldehydes proceeded in the presence of 0.

Asymmetric synthesis of 1-aryl-1,2-ethanediols from arylacetylenes by palladium-catalyzed asymmetric hydrosilylation as a key step.

Double hydrosilylation of arylacetylenes with trichlorosilane catalyzed first by platinum and second by a chiral monophosphine-palladium complex generated the corresponding 1,2-bis(silyl)-1-arylethanes, the oxidation of which with hydrogen peroxide gave 1-aryl-1,2-diols of high enantiomeric purity (94-98% ee) in high yields.