Modified Chemoselective Reduction and Consecutive Regioselective Deuteration Reaction Catalyzed by B(CF).

An efficient chemoselective reduction of isatin derivatives using catalyst B(CF), benzyldimethylsilane, and HO is described. Notably, a small amount of water is shown to be a highly effective reaction promoter that decreases the reaction time and temperature for the synthesis of indolin-3-ones. Moreover, using method, excellent deuterium incorporation is achieved the catalytic α-deuteration of indolin-3-ones using B(CF) and DO.

Rhodium(II)-Catalyzed Highly Selective 1,3-Insertion Reactions Using -Sulfonyl-1,2,3-Triazoles with Heteroaryl Ethers or Heteroaryl Alcohols.

The transformation of -sulfonyl-1,2,3-triazoles insertion/rearrangement is achieved using 2-hydroxybenzimidazole or 2-alkoxybenzothiazole over 3 mol % Rh(Oct) for the synthesis of α-((1-benzo[]imidazol-2-yl)amino) ketones or ()-2-alkoxy-2-phenylethenamines. This regio- and stereoselective reaction proceeds under mild conditions, is tolerant of functional groups, and has a broad substrate scope. Notably, while the general rhodium-catalyzed reaction involves sigmatropic rearrangement from an allyl vinyl ether, the present synthetic methodology prevents rearrangement owing to the benzimidazole group, allowing access to ()-olefins.

Effect of Bio-Inspired Polymer Types on Engineering Characteristics of Cement Composites.

Cement concrete is the most commonly used building and construction material worldwide because of its many advantages. Over time, however, it develops cracks due to shrinkage and tension, which may lead to premature failure of the entire structure. Recently, the incorporation of polymers has been explored to improve the overall strength and durability of cement concrete.

Engineering Characteristics of Cement Composites Containing a Chitosan-Based Polymer and Steel Slag Aggregates.

Recently, sustainable development has attracted significant global attention. Toward this, several studies have been performed on the development of alternative aggregates for mortar or concrete to prevent environmental damage and rapid depletion of natural aggregates. In this study, we investigated the applicability of a chitosan-based polymer (CBP), a biomimetic polymer, to cement mortar using steel slag as a fine aggregate.

Strength, Carbonation Resistance, and Chloride-Ion Penetrability of Cement Mortars Containing Catechol-Functionalized Chitosan Polymer.

There have been numerous recent studies on improving the mechanical properties and durability of cement composites by mixing them with functional polymers. However, research into applying modified biopolymer such as catechol-functionalized chitosan to cement mortar or concrete is rare to the best of our knowledge. In this study, catechol-functionalized chitosan (Cat-Chit), a well-known bioinspired polymer that imitates the basic structures and functions of living organisms and biological materials in nature, was synthesized and combined with cement mortar in various proportions.

Simulated and Experimental Investigation of the Mechanical Properties and Solubility of 3D-Printed Capsules for Self-Healing Cement Composites.

In the concrete industry, various R&D efforts have been devoted to self-healing technology, which can maintain the long-term performance of concrete structures, which is important in terms of sustainable development. Cracks in cement composites occur and propagate because of various internal and external factors, reducing the composite's stability. Interest in "self-healing" materials that can repair cracks has led researchers to embed self-healing capsules in cement composites.

Synthesis of Six-Membered Spiro Azacyclic Oxindole Derivatives via a One-Pot Process of Umpolung Allylation/Aza-Prins Cyclization.

An unprecedented synthetic approach involving umpolung allylation/aza-Prins cyclization of -2,2,2-trifluoroethylisatin ketimines is described. The reactions proceed smoothly with allyl bromide in the presence of 1,8-diazabicyclo[5.4.

B(CF)-Catalyzed Highly Chemoselective Reduction of Isatins: Synthesis of Indolin-3-ones and Indolines.

A chemo- and site-selective reduction reaction of isatin derivatives using catalyst B(CF) and hydrosilanes is described. This transformation is operationally simple, proceeds under mild conditions, and is resistant to various functional groups. Thus, this efficient reaction using a combination of B(CF) and BnMeSiH or B(CF) and EtSiH could potentially be utilized to produce various indolin-3-ones and indolines, without the need for multistep procedures and metal catalysis conditions.

Synthesis of Spiro[oxindole-3,2'-pyrrolidine] Derivatives from Benzynes and Azomethine Ylides through 1,3-Dipolar Cycloaddition Reactions.

A novel synthetic strategy employing benzyne and azomethine ylides for the construction of spiro[oxindole-3,2'-pyrrolidine] derivatives has been achieved in good yields. The ketimines obtained from the condensation of isatins with CFCHNH react with benzyne in the presence of weak bases such as TBAF or TBAT. This mild practical 1,3-dipolar cycloaddition provides an efficient route to access biologically active compounds.

Three-Component Reactions of Arynes, Amines, and Nucleophiles via a One-Pot Process.

An unprecedented three-component reaction of arynes, tertiary amines, and nucleophiles has been demonstrated through ammonium salt intermediates. This protocol allows access to tertiary aniline derivatives containing the piperazine motif in good-to-excellent yields. Expansively, this reaction can produce biologically important 2-(4-phenylpiperazin-1-yl)ethyl-containing molecules using arynes, 1,4-diazabicyclo(2.

Spirobifluorene Core-Based Novel Hole Transporting Materials for Red Phosphorescence OLEDs.

Two new hole transporting materials, named and , were designed and synthesized in significant yields using the well-known Buchwald Hartwig and Suzuki cross- coupling reactions. Both materials showed higher decomposition temperatures (over 450 °C) at 5% weight reduction and exhibited a higher glass transition temperature of 180 °C. Red phosphorescence-based OLED devices were fabricated to analyze the device performances compared to Spiro-NPB and NPB as reference hole transporting materials.

Synthesis of Bridged Cyclopentane Derivatives by Catalytic Decarbonylative Cycloaddition of Cyclobutanones and Olefins.

Herein, we report an intramolecular rhodium-catalyzed decarbonylative coupling between cyclobutanones and alkenes that proceeds by C-C activation and provides a distinct approach to a diverse range of saturated bridged cyclopentane derivatives. In this reaction, cyclobutanones serve as cyclopropane surrogates, reacting in a formal (4+2-1) transformation. To demonstrate the efficacy of this method, it was applied in a concise synthesis of the antifungal drug Tolciclate.

Efficient Hole-Transporting Materials with Triazole Core for High-Efficiency Perovskite Solar Cells.

Efficient hole-transporting materials (HTMs), TAZ-[MeOTPA]2 and TAZ-[MeOTPATh]2 incorporating two electron-rich diphenylamino side arms, through direct linkage or thiophen bridges, respectively, on the C3- and C5-positions of a 4-phenyl-1,2,4-triazole core were synthesized. These synthetic HTMs with donor-acceptor type molecular structures exhibited effective intramolecular charge transfer for improving the hole-transporting properties. The structural modification of HTMs by thiophene bridging might increase intermolecular π-π stacking in the solid state and afford a better spectral response because of their increased π-conjugation length.

Cooperative activation of cyclobutanones and olefins leads to bridged ring systems by a catalytic [4 + 2] coupling.

Bridged ring systems are widely found in natural products, and successful syntheses of them frequently feature intramolecular Diels-Alder reactions. These reactions are subclassified as either type I or type II depending on how the diene motif is tethered to the rest of the substrate (type I are tethered at the 1-position of the diene and type II at the 2-position). Although the type I reaction has been used with great success, the molecular scaffolds accessible by the type II reactions are limited by the strain inherent in the formation of an sp(2) carbon at a bridgehead position.

Highly enantioselective Rh-catalyzed carboacylation of olefins: efficient syntheses of chiral poly-fused rings.

Here we report the first highly enantioselective Rh-catalyzed carboacylation of olefins via C-C bond activation of benzocyclobutenones. Good yields and excellent enantioselectivities (92-99% ee, 14 examples) were obtained for substrates with various steric and electronic properties. In addition, fully saturated poly-fused rings were prepared from the carboacylation products through a challenging catalytic reductive dearomatization approach.

Electron-rich anthracene semiconductors containing triarylamine for solution-processed small-molecule organic solar cells.

New electron-rich anthracene derivatives containing triarylamine hole stabilizers, 2,6-bis[5,5'-bis(N,N'-diphenylaniline)-2,2'-bithiophen-5-yl]-9,10-bis-[(triisopropylsilyl)ethynyl]anthracene (TIPSAntBT-TPA) and 2,6-bis(5,5'-bis{4-[bis(9,9-dimethyl-9H-fluoren-2-yl)amino]phenyl}-2,2'-bithiophen-5-yl)-9,10-bis-[(triisopropylsilyl)ethynyl]anthracene (TIPSAntBT-bisDMFA), linked with π-conjugated bithiophene bridges, were synthesized and their photovoltaic characteristics were investigated in solution-processed small-molecule organic solar cells (SMOSCs). These new materials exhibited superior intramolecular charge transfer from triarylamine to anthracene, leading to a more electron-rich anthracene core that facilitated electron transfer into phenyl-C(61)-butyric acid methyl ester. Compared with TIPSAntBT and triarylamine, these materials show a threefold improvement in hole-transporting properties and better photovoltaic performance in solution-processed SMOSCs, with the best power conversion efficiency being 2.

Total synthesis of (-)-amphidinolide K.

Macrolide magic: An enyne cross-metathesis reaction of an alkynyl boronate with an alkene derivative as well as a radical cyclization reaction of a homopropargylic beta-alkoxyacrylate are the key transformations in the total synthesis of the cytotoxic macrolide (-)-amphidinolide K.

Total synthesis of (-)-blepharocalyxin D.

[reaction: see text] The Prins cyclization strategy was successfully applied in the total synthesis of (-)-blepharocalyxin D, a cytotoxic dimeric diarylheptanoid isolated from Alpinia blepharocalyx.