Ni-catalyzed enantioconvergent deoxygenative reductive cross-coupling of unactivated alkyl alcohols and aryl bromides.

Transition metal-catalyzed enantioconvergent cross-coupling of an alkyl precursor presents a promising method for producing enantioenriched C(sp) molecules. Because alkyl alcohol is a ubiquitous and abundant family of feedstock in nature, the direct reductive coupling of alkyl alcohol and aryl halide enables efficient access to valuable compounds. Although several strategies have been developed to overcome the high bond dissociation energy of the C - O bond, the asymmetric pattern remains unknown.

Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis.

The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable and potentially versatile approach is the coupling of a C-C bond through an outer-sphere mechanism, accompanied by the realization of enantiocontrol through cooperative catalysis; however, examples of such processes are yet to be identified. Herein, we present such a method for creating different compounds with quaternary stereocenters by photoredox/Fe/chiral primary amine triple catalysis.

Hardware Trojan Attacks on the Reconfigurable Interconnections of Field-Programmable Gate Array-Based Convolutional Neural Network Accelerators and a Physically Unclonable Function-Based Countermeasure Detection Technique.

Convolutional neural networks (CNNs) have demonstrated significant superiority in modern artificial intelligence (AI) applications. To accelerate the inference process of CNNs, reconfigurable CNN accelerators that support diverse networks are widely employed for AI systems. Given the ubiquitous deployment of these AI systems, there is a growing concern regarding the security of CNN accelerators and the potential attacks they may face, including hardware Trojans.

Meta-Analysis of Organic Fertilization Effects on Soil Bacterial Diversity and Community Composition in Agroecosystems.

Application of organic fertilizers or their combination with chemical fertilizers is a feasible practice for improving soil fertility and reducing soil degradation in agroecosystems, and these regulations are mainly mediated though soil microbial communities. Despite bacteria ranking among the most abundant and diverse groups of soil microorganisms, the effects of long-term organic fertilization (OF) and chemical-organic fertilization (COF) on soil bacterial diversity and community composition remain unclear. In this study, we conducted a meta-analysis and demonstrated that OF had no significant effect on bacterial alpha diversity.

Positive Effects of Organic Amendments on Soil Microbes and Their Functionality in Agro-Ecosystems.

Soil microbial characteristics are considered to be an index for soil quality evaluation. It is generally believed that organic amendments replacing chemical fertilizers have positive effects on changing microbial activity and community structure. However, their effects on different agro-ecosystems on a global scale and their differences in different environmental conditions and experimental durations are unclear.

Iron-Catalyzed Reductive Cross-Coupling of Alkyl Electrophiles with Olefins.

In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl-alkyl bond construction is central to organic synthesis, examples of iron-catalyzed alkyl-alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross-coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents.

A novel electronic nose for the detection and classification of pesticide residue on apples.

Excessive pesticide residues are a serious problem faced by food regulatory authorities, suppliers, and consumers. To assist with this challenge, this work aimed to develop a method of detecting and classifying pesticide residue on fruit samples using an electronic nose, through the application of three different data-recognition algorithms. The apple samples carried various concentrations of two known pesticides, namely cypermethrin and chlorpyrifos.

Evaluation of the freshness of rainbow trout () fillets by the NIR, E-nose and SPME-GC-MS.

A comparison study on the freshness of rainbow trout () fillets in the course of their sale was performed using near-infrared spectroscopy (NIRS), solid-phase microextraction combined with gas chromatography-mass spectrometry (SPME-GC-MS), and the electronic nose (E-nose) technique. Quantitative analysis of the volatile salt nitrogen (TVB-N) of rainbow trout fillets with different freshness using NIR combined with the partial least squares (PLS) method revealed that the predicted values of TVB-N of the samples were significantly correlated with the true values ( < 0.01).

Asymmetric Synthesis of Protected Unnatural α-Amino Acids via Enantioconvergent Nickel-Catalyzed Cross-Coupling.

Interest in unnatural α-amino acids has increased rapidly in recent years in areas ranging from protein design to medicinal chemistry to materials science. Consequently, the development of efficient, versatile, and straightforward methods for their enantioselective synthesis is an important objective in reaction development. In this report, we establish that a chiral catalyst based on nickel, an earth-abundant metal, can achieve the enantioconvergent coupling of readily available racemic alkyl electrophiles with a wide variety of alkylzinc reagents (1:1.

The Asymmetric Synthesis of Amines via Nickel-Catalyzed Enantioconvergent Substitution Reactions.

Chiral dialkyl carbinamines are important in fields such as organic chemistry, pharmaceutical chemistry, and biochemistry, serving for example as bioactive molecules, chiral ligands, and chiral catalysts. Unfortunately, most catalytic asymmetric methods for synthesizing dialkyl carbinamines do not provide general access to amines wherein the two alkyl groups are of similar size (e.g.

Quaternary stereocentres via catalytic enantioconvergent nucleophilic substitution reactions of tertiary alkyl halides.

The development of efficient methods, particularly catalytic and enantioselective processes, for the construction of all-carbon quaternary stereocentres is an important (and difficult) challenge in organic synthesis due to the occurrence of this motif in a range of bioactive molecules. One conceptually straightforward and potentially versatile approach is the catalytic enantioconvergent substitution reaction of a readily available racemic tertiary alkyl electrophile by an organometallic nucleophile; however, examples of such processes are rare. Here we demonstrate that a nickel-based chiral catalyst achieves enantioconvergent couplings of a variety of tertiary electrophiles (cyclic and acyclic α-halocarbonyl compounds) with alkenylmetal nucleophiles to form quaternary stereocentres with good yield and enantioselectivity under mild conditions in the presence of a range of functional groups.

Effects of supplemental nitrogen application on physiological characteristics, dry matter and nitrogen accumulation of winter rapeseed (Brassica napus L.) under waterlogging stress.

Waterlogging stress is a common limiting factor for winter rapeseed, which greatly affects the growth and potential production. The present study was conducted to investigate the effects of waterlogging with different durations (0day (D0), 6days (D6) and 9days (D9)) and supplemental nitrogen fertilization (N1, 0 kg ha; N2, 30 kg ha; N3, 60 kg ha and N4, 90 kg ha) on the physiological characteristics, dry matter and nitrogen accumulation in winter rapeseed (Chuanyou36). The results showed that the supplementary application of nitrogen fertilizer could effectively improve the physiological indexes of winter rapeseed in both pot and field experiments.

Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols.

Because chiral dialkyl carbinols, as well as their derived esters, are significant as intermediates and end points in fields such as organic, pharmaceutical, and biological chemistry, the development of efficient approaches to their asymmetric synthesis is an important endeavor. In this report, we describe a method for the direct catalytic enantioselective synthesis of such esters, beginning with an alkyl halide (derived from an aldehyde and an acyl bromide), an olefin, and a hydrosilane, catalyzed by nickel, an earth-abundant metal. The method is versatile, tolerating substituents that vary in size and that bear a range of functional groups.

Design of UAV Downwash Airflow Field Detection System Based on Strain Effect Principle.

Accurate measurement of the downwash flow field of plant protection unmanned aerial vehicles (UAVs) is essential for analyzing the spatial distribution of droplets. To realize on-line rapid detection of the downwash flow field of a multi-rotor UAV, a flexible polypropylene detection device based on the principle of full bridge strain effect was proposed. Its performance principle was based on the physical deformation caused by wind pressure.

Tandem Pd-Catalyzed Intermolecular Allylic Alkylation/Allylic Dearomatization Reaction of Benzoylmethyl pyridines, Pyrazines, and Quinolines.

An efficient synthesis of nitrogen-containing heterocycles via Pd-catalyzed tandem allylic alkylation and dearomatization reactions was reported. In this reaction design, heteroarenes such as pyridines, pyrazines, and quinolines serve as bis-nucleophiles by installing a benzoyl group at the C2 benzylic position. With but-2-ene-1,4-diyl dimethyl dicarbonate as the bis-electrophile, the tandem Pd-catalyzed intermolecular allylic alkylation/allylic dearomatization reaction of benzoylmethyl-substituted heteroarenes has been developed.

Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Benzene Derivatives.

Guided by the mechanistic insights from computational studies, we have developed an Ir-catalyzed asymmetric intramolecular allylic dearomatization reaction of benzene derivatives. Under the optimized conditions consisting of a readily available Ir catalyst, a series of spiro[4.5]cyclohexadiene compounds were delivered in reasonable yields (up to 79 %) with good enantioselectivity (up to 99 % ee).

[Flux Characteristics of CO, CH, and N O and their Influencing Factors in Different Types of Ditches on the Chengdu Plain].

In order to study the flux characteristics of CH, CO and NO in different ditches and their influencing factors, three types of ditches (an agricultural ditch, agricultural-living compound ditch, and living ditch) were monitored once a month from March 2014 to February 2015 using static floating chambers in the Chengdu Plain. The results showed that:① Affected by human activities, CO, CH, and NO fluxes were high in ditches and ranged from -2.26-1504.

Efficient Synthesis of N-Alkylated 4-Pyridones by Copper-Catalyzed Intermolecular Asymmetric Propargylic Amination.

Copper-catalyzed intermolecular asymmetric propargylic amination with 4-hydroxypyridines has been realized for the first time. In the presence of Cu complex derived from Pybox ligand, the N-propargylated 4-pyridones were obtained under mild reaction conditions with up to 99 % yield and 95 % ee. The Pybox ligand bearing a 4-F-phenyl substituent plays a key role for the high enantioselectivity.

Iridium-Catalyzed Intramolecular Asymmetric Allylic Alkylation of Hydroxyquinolines: Simultaneous Weakening of the Aromaticity of Two Consecutive Aromatic Rings.

Intramolecular asymmetric allylic alkylation reactions of 5- and 7-hydroxyquinoline derivatives were realized by a chiral Ir/NHC catalyst. A series of functionalized cyclic enones were afforded in excellent yields (up to 99%) and high enantioselectivity (up to 97% ee). Theoretical computations revealed that the aromaticity of the two consecutive rings of hydroxyquinoline substrates is significantly weakened.

Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization Reaction of Benzoxazoles, Benzothiazoles, and Benzimidazoles.

An iridium-catalyzed intramolecular asymmetric allylic dearomatization reaction of benzoxazoles, benzothiazoles, and benzimidazoles was developed. The reaction was found to be compatible with a wide range of five-membered-ring electron-deficient heteroaromatic compounds and furnished the corresponding dearomatized heterocycles in high yield with excellent enantioselectivity.

The fabrication of In2O3/In2S3/Ag nanocubes for efficient photoelectrochemical water splitting.

In this work, for the first time, a three-component In2O3/In2S3/Ag nanocomposite heterostructured photoanode is prepared on a F-doped SnO2 (FTO) glass substrate. The three-component photoanode exhibits significantly enhanced photoelectrochemical properties compared with the single-component (In2O3) and two-component (In2O3/In2S3 or In2O3/Ag) systems. Ag nanoparticles deposited on the surface of In2O3/In2S3 nanocubes can facilitate the separation of photogenerated charge carriers and enhance the absorption of visible light.

Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization Reaction of Pyridines, Pyrazines, Quinolines, and Isoquinolines.

The first Ir-catalyzed intramolecular asymmetric allylic dearomatization reaction of pyridines, pyrazines, quinolines, and isoquinolines has been developed. Enabled by in situ formed chiral Ir-catalyst, the dearomatized products were isolated in high levels of yield (up to 99% yield) and enantioselectivity (up to 99% ee). It is worth noting that the Me-THQphos ligand is much more efficient than other tested ligands for the dearomatization of pyrazines and certain quinolines.

Highly regio- and enantioselective synthesis of N-substituted 2-pyridones: iridium-catalyzed intermolecular asymmetric allylic amination.

The first iridium-catalyzed intermolecular asymmetric allylic amination reaction with 2-hydroxypyridines has been developed, thus providing a highly efficient synthesis of enantioenriched N-substituted 2-pyridone derivatives from readily available starting materials. This protocol features a good tolerance of functional groups in both the allylic carbonates and 2-hydroxypyridines, thereby delivering multifunctionalized heterocyclic products with up to 98% yield and 99% ee.

Catalytic asymmetric reactions by metal and chiral phosphoric acid sequential catalysis.

Catalytic asymmetric reactions promoted by metal catalysts and chiral phosphoric acids have become useful processes for the preparation of structurally diverse and complex organic compounds. This JOCSynopsis provides an overview of the most recent developments made in studies of these reactions. The paper focuses mainly on sequential catalysis and relay catalysis, which are accomplished by employing a combination of metal complexes and chiral phosphoric acids.