The authors examine the enantioselective hydrogenation of enamines and imines in metal-catalyzed transitions. The enantioselective hydrogenation of several catalysts is also studied.
“… Most transition‐metal catalysts and organocatalysts do not meet the requirements for modern industrial manufacturing processes. Their main limitation is low efficiency. The need to develop highly ...efficient catalysts and related catalytic reactions is a never‐ending challenge in synthetic chemistry …” Read more in the Editorial by Qi‐Lin Zhou.
Structural damage detection is still a challenging problem owing to the difficulty of extracting damage‐sensitive and noise‐robust features from structure response. This article presents a novel ...damage detection approach to automatically extract features from low‐level sensor data through deep learning. A deep convolutional neural network is designed to learn features and identify damage locations, leading to an excellent localization accuracy on both noise‐free and noisy data set, in contrast to another detector using wavelet packet component energy as the input feature. Visualization of the features learned by hidden layers in the network is implemented to get a physical insight into how the network works. It is found the learned features evolve with the depth from rough filters to the concept of vibration mode, implying the good performance results from its ability to learn essential characteristics behind the data.
•A novel aminothiazole-based cyclotriphosphazene derivate (HTACP) is successfully synthesized.•HTACP shows high efficiency for simultaneously enhancing flame retardancy and smoke suppression for ...epoxy resin.•HTACP presents a special bi-phase flame retardant mechanism.
There is a need to develop halogen-free flame retardants for epoxy resin (EP) to reduce the fire risks. Cyclotriphosphazene-based derivatives have been proved to be effective phosphorous-containing flame retardants. This article demonstrates the preparation and application of a novel aminothiazole-based cyclotriphosphazene derivate (hexathiazoleaminocyclotriphosphazene, HTACP) for EP. After characterizing by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance, and high-resolution mass spectroscopy, HTACP is utilized as a reactive flame retardant for EP. HTACP effectively inhibits the decomposition of EP and improves the char yield during heating according to the thermogravimetric analysis (TGA) results. HTACP also changes the dynamic thermomechanical behaviors of EP according to dynamic mechanical analysis (DMA). With the incorporation of 5 wt% HTACP, EP passes UL-94 V-0 rating during the vertical flame testing and obtains an increased limiting oxygen index of 28.5% with only 0.73% phosphorous content. The cone calorimeter testing results show that HTACP endows EP with beyond 50% reduction of peak heat release rate and total smoke production. The results of smoke density chamber tests also prove the excellent smoke-suppression effects for EP. Furthermore, scanning electron micrograph, X-ray photoelectron spectroscopy, TG-FTIR, and pyrolysis gas chromatography/mass spectrometry are used to analyze the chars and pyrolysis behaviors of EP/HTACP. The phosphazene structure in HTACP molecule is left in the condensed phase, which promotes forming protective chars, while the multiple nitrogen- and sulfur-containing volatiles derives from aminothiazole groups act dilution effects in the flame zone. This novel aminothiazole-based cyclotriphosphazene shows a high efficiency for reducing fire hazards of EP through a bi-phase mechanism.
To compare the different actions of the two representative transition metal cations of Co2+ and Ni2+ in layered double hydroxides (LDHs), CoAl-LDH and NiAl-LDH intercalated with CO32− were ...synthesized, and the chemical structures, microstructures, and surface areas thereof were successfully characterized. Then, the two LDHs were utilized as flame retardants and smoke suppressants for silicone foam (SiF). The densities, flame retardancy, smoke suppression, thermal stabilities, and compressive strengths of the two SiF/LDHs nanocomposites were investigated. The introduction of LDHs slightly decreased the density of SiF due to the catalytic actions of Co and Ni during the foaming process of SiF. With respect to the flame retardancy, the addition of only 1 phr of either CoAl-LDH or NiAl-LDH could effectively improve the limiting oxygen index of SiF from 28.7 to 29.6%. Based on the results of vertical flame testing and a cone calorimeter test, the flame retardancy and fire safety of the SiF were effectively enhanced by the incorporation of LDHs. In addition, owing to the good catalytic action and large specific surface area (NiAl-LDH: 174.57 m2 g−1; CoAl-LDH: 51.47 m2 g−1), NiAl-LDH revealed higher efficiencies of flame retardancy and smoke suppression than those of CoAl-LDH. According to the results of energy-dispersive X-ray spectroscopy, Co and Ni participated in the formation of protective char layers, which inhibited the release of SiO2 into the gas phase. Finally, the influences on the thermal decomposition and compressive strength for SiF resulting from the addition of LDHs are discussed.
Air pollution is a world public health problem. Particulate matter (PM), a mix of solid and liquid particles in the air, becomes an increasing concern in the social and economic development of China. ...For decades, epidemiological studies have confirmed the association between fine particle pollutants and respiratory diseases. It has been reported in different populations that increased fine particulate matter (PM2.5) concentrations cause elevated susceptibility to respiratory diseases, including acute respiratory distress, asthma, chronic obstructive pulmonary disease, and lung cancer. This review will discuss the pathophysiology of PM2.5 in respiratory diseases, which are helpful for the prevention of air pollution and treatment of respiratory tract inflammatory diseases.
Transition metal-catalyzed carbene insertion into X-H bonds (X = N, O, S, and C) represents a typical carbene transfer reaction and has been widely used in organic synthesis. The ...enantioselectivity-determining step in some of these insertion reactions is the proton transfer of active intermediates such as ylides, metal enolates, or free enols. Since most of the traditional chiral transition metal catalysts tend to dissociate from these active intermediates and cannot be involved in the proton-transfer step, enantiocontrol of these insertion reactions has long been a challenging task. Since 2011, we have developed chiral spiro phosphoric acids as chiral proton-transfer shuttle (CPTS) catalysts, which have been proven to be efficient catalysts for the proton transfer of active intermediates in carbene insertion reactions. Upon combining with achiral dirhodium catalysts, the CPTS catalysts accomplish highly enantioselective insertions of N-H, S-H, and C-H bonds. Herein, a number of important chiral building blocks, including α-amino acid derivatives, α-amino ketones, α-thioesters, and α,α-diaryl acetates, were prepared with high yields and high enantioselectivities through these insertion reactions.
The development of chiral proton-transfer shuttles provides a totally new enantiocontrol strategy for transition metal-catalyzed asymmetric carbene insertion reactions.
Carbon–heteroatom bonds (C–X) are ubiquitous and are among the most reactive components of organic compounds. Therefore investigations of the construction of C–X bonds are fundamental and vibrant ...fields in organic chemistry. Transition-metal-catalyzed heteroatom–hydrogen bond (X–H) insertions via a metal carbene or carbenoid intermediate represent one of the most efficient approaches to form C–X bonds. Because of the availability of substrates, neutral and mild reaction conditions, and high reactivity of these transformations, researchers have widely applied transition-metal-catalyzed X–H insertions in organic synthesis. Researchers have developed a variety of rhodium-catalyzed asymmetric C–H insertion reactions with high to excellent enantioselectivities for a wide range of substrates. However, at the time that we launched our research, very few highly enantioselective X–H insertions had been documented primarily because of a lack of efficient chiral catalysts and indistinct insertion mechanisms. In this Account, we describe our recent studies of copper- and iron-catalyzed asymmetric X–H insertion reactions by using chiral spiro-bisoxazoline and diimine ligands. The copper complexes of chiral spiro-bisoxazoline ligands proved to be highly enantioselective catalysts for N–H insertions of α-diazoesters into anilines, O–H insertions of α-diazoesters into phenols and water, O–H insertions of α-diazophosphonates into alcohols, and S–H insertions of α-diazoesters into mercaptans. The iron complexes of chiral spiro-bisoxazoline ligands afforded the O–H insertion of α-diazoesters into alcohols and water with unprecedented enantioselectivities. The copper complexes of chiral spiro-diimine ligands exhibited excellent reactivity and enantioselectivity in the Si–H insertion of α-diazoacetates into a wide range of silanes. These transition-metal-catalyzed X–H insertions have many potential applications in organic synthesis because the insertion products, including chiral α-aminoesters, α-hydroxyesters, α-hydroxyphosphonates, α-mercaptoesters, and α-silyl esters, are important building blocks for the synthesis of biologically active compounds. The electronic properties of α-diazoesters and anilines markedly affected the enantioselectivity of N–H insertion reaction, which supports a stepwise ylide insertion mechanism. A novel binuclear spiro copper complex was isolated and fully characterized using X-ray diffraction analysis and ESI-MS analysis. The positive nonlinear effect indicated that binuclear copper complexes were the catalytically active species. The 14-electron copper centers, trans coordination model, perfect C 2-symmetric chiral pocket, and Cu–Cu interaction facilitate the performance of the chiral spiro catalysts in X–H insertion reactions.
A Ni‐catalyzed hydroarylation of styrenes and 1,3‐dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes and allylarenes under ...redox‐neutral conditions. In this hydroarylation reaction, a new strategy that uses the proton of methanol to generate the active catalyst species Ni−H was developed. The Ni‐catalyzed hydroarylation, combined with a Ir‐catalyzed C−H borylation, affords a very efficient and straightforward access to a retinoic acid receptor agonist.
OH yeah: A nickel(0)‐catalyzed hydroarylation of alkenes with organoboron reagents using an alcohol OH group as the H‐atom source is reported. The reaction offers a highly selective approach to diarylalkanes and allylarenes under redox‐neutral conditions.
Chiral carboxylic acid moieties are widely found in pharmaceuticals, agrochemicals, flavors, fragrances, and health supplements. Although they can be synthesized straightforwardly by ...transition-metal-catalyzed enantioselective hydrogenation of unsaturated carboxylic acids, because the existing chiral catalysts have various disadvantages, the development of new chiral catalysts with high activity and enantioselectivity is an important, long-standing challenge. Ruthenium complexes with chiral diphosphine ligands and rhodium complexes with chiral monodentate or bidentate phosphorus ligands have been the predominant catalysts for asymmetric hydrogenation of unsaturated acids. However, the efficiency of these catalysts is highly substrate-dependent, and most of the reported catalysts require a high loading, high hydrogen pressure, or long reaction time for satisfactory results. Our recent studies have revealed that chiral iridium complexes with chiral spiro-phosphine-oxazoline ligands and chiral spiro-phosphine-benzylamine ligands exhibit excellent activity and enantioselectivity in the hydrogenation of α,β-unsaturated carboxylic acids, including α,β-disubstituted acrylic acids, trisubstituted acrylic acids, α-substituted acrylic acids, and heterocyclic α,β-unsaturated acids. On the basis of an understanding of the role of the carboxy group in iridium-catalyzed asymmetric hydrogenation reactions, we developed a carboxy-group-directed strategy for asymmetric hydrogenation of olefins. Using this strategy, we hydrogenated several challenging olefin substrates, such as β,γ-unsaturated carboxylic acids, 1,1-diarylethenes, 1,1-dialkylethenes, and 1-alkyl styrenes in high yield and with excellent enantioselectivity. All these iridium-catalyzed asymmetric hydrogenation reactions feature high turnover numbers (up to 10000) and turnover frequencies (up to 6000 h–1), excellent enantioselectivities (greater than 95% ee with few exceptions), low hydrogen pressure (<12 atm), and operational simplicity. These features make chiral iridium catalysts superior or comparable to well-established chiral ruthenium and rhodium catalysts for asymmetric hydrogenation of unsaturated carboxylic acids. A number of chiral natural products and pharmaceuticals have been prepared by concise routes involving an iridium-catalyzed asymmetric hydrogenation of an unsaturated carboxylic acid as a key step. As part of a mechanistic study of iridium-catalyzed asymmetric hydrogenation of unsaturated acids, we isolated, for the first time, the migratory insertion intermediate in the iridium-catalyzed asymmetric hydrogenation of olefins, and this result strongly supports the involvement of an Ir(III)/Ir(V) catalytic cycle. The rigid, bulky scaffold of the chiral spiro-P,N-ligands of the catalysts not only prevents them from undergoing deactivating aggregation under the hydrogenation conditions but also is responsible for the efficient chiral induction. The carboxy group of the substrate acts as an anchor to ensure coordination of the substrate to the iridium center of the catalyst during the reaction and makes the hydrogenation proceed smoothly.
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