Palladium(0) π-Lewis Base Catalysis: Concept and Development.

The development of a new catalytic strategy plays a vital role in modern organic chemistry since it permits bond formation in an unprecedented and more efficient manner. Although the application of preformed metal complexes as π-base-activated reagents have enabled diverse transformations elegantly, the concept and strategy by directly utilizing transition metals as efficient π-Lewis base catalysts remain underdeveloped, especially in the field of asymmetric catalysis. Here, we outline our perspective on the discovery of palladium(0) as an efficient π-Lewis base catalyst, which is capable of increasing the highest occupied molecular orbital (HOMO) energy of both electron-neutral and electron-deficient 1,3-dienes and 1,3-enynes upon flexible η2-complexes formed in situ and resultant π-backdonation. Thus, fruitful carbon-carbon-forming reactions with diverse electrophiles can be achieved enantioselectively in a vinylogous addition pattern, which is conceptually different from the classical oxidative cyclization mechanism. Emphasis will be given to the concept and mechanism elucidation, catalytic features, and reaction design together with perspective on the further development of this emerging field.

Pd(0)-Catalyzed Asymmetric Cyclization/Coupling Cascade of Alkyne-Tethered Unsaturated Carbonyls: Development and Mechanism Elucidation.

While the Pd(0)-catalyzed cyclization of alkyne-tethered unsaturated carbonyl substrates has been reported, the mechanism has not been well elucidated, and the potential asymmetric version remains to be developed. Here, we disclose that a chiral Pd(0) complex can efficiently promote the desymmetrizative cyclization of alkyne-tethered cyclohexadienones in CH3OH, and the resultant Pd(II) intermediates further undergo an array of tandem coupling reactions, including Suzuki, Sonogashira, and even chemoselective reduction by CH3OH in the absence of additional coupling partners. As a result, a broad spectrum of hydrobenzofuran derivatives, having a tetra- or trisubstituted exo-alkene motif, is constructed with moderate to outstanding enantioselectivity in an exclusive cis-difunctionalization pattern. In addition, this enantioselective protocol can be well expanded to linear alkyne-tethered unsaturated carbonyls, and a new desymmetrizative and asymmetric cyclization/coupling cascade of bis-alkyne-tethered enones is further realized efficiently, furnishing diversely structured frameworks with high stereoselectivity. Moreover, kinetic transformation for various racemic alkyne-tethered enones can be accomplished under similar catalytic conditions, and unusual kinetic reactions by chemoselectively undertaking Suzuki or Sonogashira coupling, or reduction by CH3OH, occur sequentially, finally yielding two types of chiral products, both with high enantioselectivity via either ligand- or substrate-based control. The experimental results demonstrate that the current Pd(0)-based strategy is superior to the classical Pd(II)-catalyzed carbopalladation/cyclization process of the identical substrates with regard to enantioselectivity and synthetic versatility. Moreover, density functional theory calculations are conducted to rationalize the Pd(0)-catalyzed oxidative cyclometalation pathway in the key cyclization step, which leads to the observed cis-difunctionalized products exclusively.

SUGP2 p.(Arg639Gln) variant is involved in the pathogenesis of hemochromatosis via the CIRBP/BMPER signaling pathway.

Pathogenic variants in HFE and non-HFE genes have been identified in hemochromatosis in different patient populations, but there are still a certain number of patients with unexplained primary iron overload. We recently identified in Chinese patients a recurrent p.(Arg639Gln) variant in SURP and G-patch domain containing 2 (SUGP2), a potential mRNA splicing-related factor. However, the target gene of SUGP2 and affected iron-regulating pathway remains unknown. We aimed to investigate the pathogenicity and underlying mechanism of this variant in hemochromatosis. RNA-seq analysis revealed that SUGP2 knockdown caused abnormal alternative splicing of CIRBP pre-mRNA, resulting in an increased normal splicing form of CIRBP V1, which in turn increased the expression of BMPER by enhancing its mRNA stability and translation. Furthermore, RNA-protein pull-down and RNA immunoprecipitation assays revealed that SUGP2 inhibited splicing of CIRBP pre-mRNA by a splice site variant at CIRBP c.492 and was more susceptible to CIRBP c.492 C/C genotype. Cells transfected with SUGP2 p.(Arg639Gln) vector showed up-regulation of CIRBP V1 and BMPER expression and down-regulation of pSMAD1/5 and HAMP expression. CRISPR-Cas9 mediated SUGP2 p.(Arg622Gln) knock-in mice showed increased iron accumulation in the liver, higher total serum iron, and decreased serum hepcidin level. A total of 10 of 54 patients with hemochromatosis (18.5%) harbored the SUGP2 p.(Arg639Gln) variant and carried CIRBP c.492 C/C genotype, and had increased BMPER expression in the liver. Altogether, the SUGP2 p.(Arg639Gln) variant down-regulates hepcidin expression through the SUGP2/CIRBP/BMPER axis, which may represent a novel pathogenic factor for hemochromatosis.

Tiny clue reveals the general trend: a bibliometric and visualized analysis of renal microcirculation.

BACKGROUND: Renal microcirculation plays a pivotal role in kidney function by maintaining structural and functional integrity, facilitating oxygen and nutrient delivery, and waste removal. However, a thorough bibliometric analysis in this area remains lacking. Therefore, we aim to provide valuable insights through a bibliometric analysis of renal microcirculation literature using the Web of Science database. METHODS: We collected renal microcirculation-related publications from the Web of Science database from January 01, 1990, to December 31, 2022. The co-authorship of authors, organizations, and countries/regions was analyzed with VOSviewer1.6.18. The co-occurrence of keywords and co-cited references were analyzed using CiteSpace6.1.R6 software to generate visualization maps. Additionally, burst detection was applied to keywords and cited references to forecast research hotspots and future trends. RESULTS: Our search yielded 7462 publications, with the American Journal of Physiology-Renal Physiology contributing the most articles. The United States, Mayo Clinic, and Lerman Lilach O emerged with the highest publication count, indicating their active collaborations. 'Type 2 diabetes' was the most significant keyword cluster, and 'diabetic kidney disease' was the largest cluster of cited references. 'Cardiovascular outcome' and 'diabetic kidney diseases' were identified as keywords in their burst period over the past three years. CONCLUSION: Our bibliometric analysis illuminates the contours of nephrology and microcirculation research, revealing a landscape ripe for challenges and the seeds of future scientific innovation. While the trends discerned from the literature emerging opportunities in diagnostic innovation, renal microcirculation research, and precision medicine interventions, their translation to clinical practice is anticipated to be a deliberate process.

Prediction and visualization of moisture content in Tencha drying processes by computer vision and deep learning.

BACKGROUND: It is important to monitor and control the moisture content throughout the Tencha drying processing procedure so that its quality is ensured. Workers often rely on their senses to perceive the moisture content, leading to relative subjectivity and low reproducibility. Traditional drying methods, which are used for measuring moisture content, are destructive to samples. This research was conducted using computer vision combined with deep learning to detect moisture content during the Tencha drying process. Different color space components of Tencha drying sample images were first extracted by computer vision. The color components were preprocessed using MinMax and Z score. Subsequently, one-dimensional convolutional neural networks (1D-CNN), partial least squares, and backpropagation artificial neural networks models were built and compared. RESULTS: The 1D-CNN model and Z score preprocessing achieved superior predictive accuracy, with correlation coefficient of prediction (Rp) = 0.9548 for moisture content. The migration of moisture content during the Tencha drying process was eventually visualized by mapping its spatial and temporal distributions. CONCLUSION: The results indicated that computer vision combined with 1D-CNN was feasible for moisture prediction during the Tencha drying process. This study provides technical support for the industrial and intelligent production of Tencha. © 2024 Society of Chemical Industry.

Time series prediction of insect pests in tea gardens.

BACKGROUND: Tea-garden pest control is crucial to ensure tea quality. In this context, the time-series prediction of insect pests in tea gardens is very important. Deep-learning-based time-series prediction techniques are advancing rapidly but research into their use in tea-garden pest prediction is limited. The current study investigates the time-series prediction of whitefly populations in the Tea Expo Garden, Jurong City, Jiangsu Province, China, employing three deep-learning algorithms, namely Informer, the Long Short-Term Memory (LSTM) network, and LSTM-Attention. RESULTS: The comparative analysis of the three deep-learning algorithms revealed optimal results for LSTM-Attention, with an average root mean square error (RMSE) of 2.84 and average mean absolute error (MAE) of 2.52 for 7 days' prediction length, respectively. For a prediction length of 3 days, LSTM achieved the best performance, with an average RMSE of 2.60 and an average MAE of 2.24. CONCLUSION: These findings suggest that different prediction lengths influence model performance in tea garden pest time series prediction. Deep learning could be applied satisfactorily to predict time series of insect pests in tea gardens based on LSTM-Attention. Thus, this study provides a theoretical basis for the research on the time series of pest and disease infestations in tea plants. © 2024 Society of Chemical Industry.

ZnO@Ag-Functionalized Paper-Based Microarray Chip for SERS Detection of Bacteria and Antibacterial and Photocatalytic Inactivation.

Bacterial infections caused by pathogenic microorganisms have become a serious, widespread health concern. Thus, it is essential and required to develop a multifunctional platform that can rapidly and accurately determine bacteria and effectively inhibit or inactivate pathogens. Herein, a microarray SERS chip was successfully synthesized using novel metal/semiconductor composites (ZnO@Ag)-ZnO nanoflowers (ZnO NFs) decorated with Ag nanoparticles (Ag NPs) arrayed on a paper-based chip as a supporting substrate for in situ monitoring and photocatalytic inactivation of pathogenic bacteria. Typical Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli and Vibrio parahemolyticus were selected as models. Partial least-squares discriminant analysis (PLS-DA) was performed to minimize the dimensionality of SERS spectra data sets and to develop a cost-effective identification model. The classification accuracy was 100, 97.2, and 100% for S. aureus, E. coli, and V. parahemolyticus, respectively. The antimicrobial activity of ZnO@Ag was proved by the microbroth dilution method, and the minimum inhibitory concentrations (MICs) of S. aureus, E. coli, and V. parahemolyticus were 40, 50, and 55 µg/mL, respectively. Meanwhile, it demonstrated remarkable photocatalytic performance under natural sunlight for the inactivation of pathogenic bacteria, and the inactivation rates for S. aureus, E. coli, and V. parahemolyticus were 100, 97.03 and 97.56%, respectively. As a result, the microarray chip not only detected the bacteria with high sensitivity but also confirmed the antibacterial and photocatalytic sterilization properties. Consequently, it offers highly prospective strategies for foodborne diseases caused by pathogenic bacteria.

The Effects of Dialysis Modality and Emotional Distress on Fatigue in Patients Undergoing Dialysis.

INTRODUCTION: Fatigue is a common but often overlooked symptom in dialysis patients. Factors affecting fatigue in dialysis patients are currently unclear. There are few studies on the effects of mental factors and dialysis modality on fatigue. This study aims to explore the potential relationship between fatigue and insomnia, as well as psychiatric disorders such as anxiety and depression among patients who undergo peritoneal dialysis (PD) or hemodialysis (HD). METHODS: There were 96 HD patients and 160 PD patients at our hospital who voluntarily participated in the survey. A questionnaire survey was conducted to gather general characteristics of the patients and to evaluate fatigue, sleep quality, anxiety, and depression levels among PD and HD patients. RESULTS: The overall fatigue score was 53.83 ± 14.22 for the PD group and 57.92 ± 16.35 for the HD group. Notably, the fatigue level was lower in the PD group compared to the HD group (p < 0.05). Univariate analysis indicated that fatigue was associated with occupational status and income in the PD group, as well as educational level and income in the HD group (p < 0.05). Correlation analysis revealed that patients in both groups who were older and had higher scores for insomnia, anxiety, and depression experienced more severe fatigue. Moreover, body mass index was positively correlated with fatigue status in the PD group, while duration of dialysis showed a positive association with fatigue in the HD group. Multivariate regression analysis identified income and depression as major factors influencing fatigue in the PD group, and duration of dialysis, income, and depression in the HD group. CONCLUSION: Patients who undergo dialysis exhibit high levels of fatigue, with the severity of fatigue being less pronounced in the PD group compared to the HD group. Fatigue in these patients is associated with the duration of dialysis, income level, and presence of depression.

Advances in surface-enhanced Raman spectroscopy technology for detection of foodborne pathogens.

Rapid control and prevention of diseases caused by foodborne pathogens is one of the existing food safety regulatory issues faced by various countries and has received wide attention from all sectors of society. The development of rapid and reliable detection methods for foodborne pathogens remains a hot research area for food safety and public health because of the limitations of complex steps, time-consuming, low sensitivity, or poor selectivity of commonly used methods. Surface-enhanced Raman spectroscopy (SERS), as a novel spectroscopic technique, has the advantages of high sensitivity, selectivity, rapid and nondestructive detection and has exhibited broad application prospects in the determination of pathogenic bacteria. In this study, the enhancement mechanisms of SERS are briefly introduced, then the characteristics and properties of liquid-phase, rigid solid-phase, and flexible solid-phase are categorized. Furthermore, a comprehensive review of the advances in label-free or label-based SERS strategies and SERS-compatible techniques for the detection of foodborne pathogens is provided, and the advantages and disadvantages of these methods are reviewed. Finally, the current challenges of SERS technology applied in practical applications are listed, and the possible development trends of SERS in the field of foodborne pathogens detection in the future are discussed.

Copper-Catalyzed Aryne Insertion into the Carbon-Iodine Bond of Heteroaryl Iodides.

Aryne insertions into the carbon-iodine bond of heteroaryl iodides has been achieved for the first time. This novel reaction provides an efficient pathway for the synthesis of valuable building blocks 2-iodoheterobiaryls from heteroaryl iodides and o-silylaryl triflates in excellent regioselectivity. The copper(I) catalyst, which bears a N-heterocyclic carbene (NHC) ligand, is essential to accomplish the reaction. Control reactions and DFT calculations indicate that the coordination of copper, as a Lewis acid, with nitrogen atoms of heteroaryl iodides mediates the insertion of arynes into heteroaryl carbon-iodine bonds.

Palladium-Catalyzed Inverse and Normal Dehydrogenative Aza-Morita-Baylis-Hillman Reactions with γ,δ-Unsaturated Compounds.

σ-Lewis base-catalyzed regio- and enantioselective aza-Morita-Baylis-Hillman (MBH) reaction of α,ß,γ,δ-unsaturated systems remains a challenge due to the intrinsic covalent activation mode. Here we demonstrate that a Pd0 complex can mediate the dehydrogenative reaction of γ,δ-unsaturated compounds to give corresponding electron-poor dienes, which further undergo δ-regioselective umpolung Friedel-Crafts-type addition to imines via auto-tandem Pd0 -π-Lewis base catalysis. After ß-H elimination of in situ formed PdII -complexes, unprecedented and chemically inverse aza-MBH-type adducts are finally furnished with fair to outstanding enantioselectivity, and a diversity of functional groups and both ketimine and aldimine acceptors can be well tolerated. Moreover, switchable α-regioselective normal aza-MBH-type reaction also can be realized by tuning catalytic conditions, whereas moderate to good enantioselectivity with low to excellent Z/E-selectivity is attained.

Asymmetric Formal Nucleophilic o-Cresolylation with Morita-Baylis-Hillman Carbonates of 2-Cyclohexenones via Palladium Catalysis.

Here we report an asymmetric formal nucleophilic o-cresolylation reaction with the Morita-Baylis-Hillman (MBH) carbonates from 2-cyclohexanones and diverse aldehydes under palladium catalysis, by in situ generation of electron-neutral and HOMO-raised η2-Pd(0)-dienone complexes via an oxidative insertion/π-σ-isomerization/ß-H elimination activation sequence. The subsequent umpolung vinylogous addition to a variety of imines is realized upon Pd(0)-mediated π-Lewis base catalysis, finally furnishing o-cresolylated products followed by another cascade of a π-σ-isomerization/ß-H elimination/aromatization process. Moderate to excellent diastereo- and enantioselectivity are achieved for substantial substrate assemblies by employing a newly designed bulky chiral phosphonamidite ligand, and the resultant multifunctional products can be facilely elaborated to access diverse enantioenriched architectures. In addition, the catalytic reaction pathway is finely illuminated by control experiments.

Use of (E,E)-Dienoic Acids as Switchable (E,E)- and (Z,E)-Dienyl Anion Surrogates via Ligand-Controlled Palladium Catalysis.

Carboxylic acids are not readily applied as carbon-based nucleophiles due to their intrinsic acidic group. Here, we demonstrate that free (E,E)-2,4-dienoic acids form electron-neutral and highest occupied molecular orbital-raised η2-complexes with Pd(0) and undergo Friedel-Crafts-type additions to imines with exclusive α-regioselectivity, giving formal dienylated products after decarboxylation. Unusual and switchable (E,E)- and (Z,E)-selectivity, along with excellent enantioselectivity, is achieved via ligand-controlled outer-sphere or inner-sphere reaction modes, respectively, which are well supported by comprehensive density functional theory calculation studies. An unprecedented formal reductive Mannich reaction between (E,E)-dienoic acids and imines is also developed to furnish enantioenriched ß-amino acid derivatives.

Brain-Penetration and Neuron-Targeting DNA Nanoflowers Co-Delivering miR-124 and Rutin for Synergistic Therapy of Alzheimer's Disease.

Alzheimer disease (AD) is the leading cause of dementia that affects millions of old people. Despite significant advances in the understanding of AD pathobiology, no disease modifying treatment is available. MicroRNA-124 (miR-124) is the most abundant miRNA in the normal brain with great potency to ameliorate AD-like pathology, while it is deficient in AD brain. Herein, the authors develop a DNA nanoflowers (DFs)-based delivery system to realize exogenous supplementation of miR-124 for AD therapy. The DFs with well-controlled size and morphology are prepared, and a miR-124 chimera is attached via hybridization. The DFs are further modified with RVG29 peptide to simultaneously realize brain-blood barrier (BBB) penetration and neuron targeting. Meanwhile, Rutin, a small molecular ancillary drug, is co-loaded into the DFs structure via its intercalation into the double stranded DNA region. Interestingly, Rutin could synergize miR-124 to suppress the expression of both BACE1 and APP, thus achieving a robust inhibition of amyloid ß generation. The nanosystem could pro-long miR-124 circulation in vivo, promote its BBB penetration and neuron targeting, resulting in a significant increase of miR-124 in the hippocampus of APP/PS1 mice and robust therapeutic efficacy in vivo. Such a bio-derived therapeutic system shows promise as a biocompatible nanomedicine for AD therapy.

Discovery of a pyrano[2,3-b]pyridine derivative YX-2102 as a cannabinoid receptor 2 agonist for alleviating lung fibrosis.

BACKGROUND: Pharmacological modulation of cannabinoid 2 receptor (CB2R) is a promising therapeutic strategy for pulmonary fibrosis (PF). Thus, to develop CB2R selective ligands with new chemical space has attracted much research interests. This work aims to discover a novel CB2R agonist from an in-house library, and to evaluate its therapeutic effects on PF model, as well as to disclose the pharmacological mechanism. METHODS: Virtual screening was used to identify the candidate ligand for CB2R from a newly established in-house library. Both in vivo experiments on PF rat model and in vitro experiments on cells were performed to investigate the therapeutic effects of the lead compound and underlying mechanism. RESULTS: A "natural product-like" pyrano[2,3-b]pyridine derivative, YX-2102 was identified that bound to CB2R with high affinity. Intraperitoneal YX-2102 injections significantly ameliorated lung injury, inflammation and fibrosis in a rat model of PF induced by bleomycin (BLM). On one hand, YX-2102 inhibited inflammatory response at least partially through modulating macrophages polarization thereby exerting protective effects. Whereas, on the other hand, YX-2102 significantly upregulated CB2R expression in alveolar epithelial cells in vivo. Its pretreatment inhibited lung alveolar epithelial-to-mesenchymal transition (EMT) in vitro and PF model induced by transforming growth factor beta-1 (TGF-ß1) via a CB2 receptor-dependent pathway. Further studies suggested that the Nrf2-Smad7 pathway might be involved in. CONCLUSION: These findings suggest that CB2R is a potential target for PF treatment and YX-2102 is a promising CB2R agonist with new chemical space.

An Oxidant- and Catalyst-Free Electrooxidative Cross-Coupling Approach to Synthesize meso-Substituted Porphyrin Derivatives.

The synthesis of porphyrin and chlorin derivatives has attracted significant attention due to their numerous applications. Herein, we report an environment friendly oxidant- and catalyst-free electrooxidative cross-coupling approach for multiple coupling reactions to synthesize meso C-N, C-O, and C-S substituted porphyrin and chlorin derivatives. For C-N cross-coupling reactions, diaminated porphyrins were obtained as the main products, while using 4-bromo-2,6-dimethyl aniline resulted in monoaminated product. Similarly, electrochemical catalysis of porphyrins with phenol and thiophene produced meso-disubstituted porphyrins in moderate yields under a smaller current. Chlorins were also applicable, and 20-substituted products were efficiently produced regioselectively. To the best of our knowledge, this work represents the first example of electrooxidative C-X cross-coupling of porphyrins and chlorins.

Highly diastereoselective synthesis of benzothiazolo[3,2-a]pyridines via [4 + 2] annulation reaction of 2-vinylbenzothiazoles and azlactones.

An efficient AgOTf-catalyzed [4 + 2] annulation reaction of 2-vinylbenzothiazoles and azlactones was successfully performed under mild reaction conditions. With this approach, a series of novel benzothiazolo[3,2-a]pyridine derivatives was readily obtained in good to excellent yields (68-96%), with high diastereoselectivities and tolerating quite a broad scope of substituents. By using chiral phosphoric acid catalyst, the desired products were obtained in high enantioselectivities, up to -94%. This methodology provides a rapid and useful method for constructing fused benzothiazole derivatives.

Development of cobalt oxyhydroxide-aptamer-based upconversion sensing nano-system for the rapid detection of Staphylococcus aureus.

Staphylococcus aureus (S. aureus) is a common pathogen that is dangerous to humans' health. Herein, a novel upconversion fluorescent biosensor based on fluorescence resonance energy transfer from aptamer-labeled upconversion nanoparticles (UCNPs-apt) as donor and cobalt oxyhydroxide (CoOOH) nanosheets as acceptor was designed to detect S. aureus in complex matrices. The principle of the work relies on fluorescence resonance energy transfer as UCNPs-apt can self-assemble on CoOOH nanosheet surfaces by van der Waals forces to effectively quench the fluorescence. When S. aureus was added, the aptamer was able to preferentially capture the target, resulting in the dissociation of donor and acceptor and the recovery of fluorescence. The structure and morphology of the nanostructures were assigned in detail by a series of characterizations, and the energy transfer mechanism was evaluated by time-resolved lifetime measurements. Under the optimal conditions, a linear calibration plot was obtained in a concentration range of 45-4.5 × 106 CFU/mL with a limit of detection of 15 CFU/mL. In addition, the proposed biosensor was used for S. aureus detection in real samples (e.g., pork, beef), and the detection result showed no significant difference (p > 0.05) compared with the conventional plate count approach. Hence, the fabricated biosensor holds a potential application for S. aureus in food analysis and public health.

Discovery of Novel Non-Oxime Reactivators Showing In Vivo Antidotal Efficiency for Sarin Poisoned Mice.

A family of novel efficient non-oxime compounds exhibited promising reactivation efficacy for VX and sarin inhibited human acetylcholinesterase was discovered. It was found that aromatic groups coupled to Mannich phenols and the introduction of imidazole to the ortho position of phenols would dramatically enhance reactivation efficiency. Moreover, the in vivo experiment was conducted, and the results demonstrated that Mannich phenol L10R1 (30 mg/kg, ip) could afford 100% 48 h survival for mice of 2*LD50 sarin exposure, which is promising for the development of non-oxime reactivators with central efficiency.

Palladium-Catalyzed Modular and Enantioselective cis-Difunctionalization of 1,3-Enynes with Imines and Boronic Reagents.

Here we report that a palladium(0) complex can mediate the unprecedented intermolecular coupling reaction of 1,3-enynes and N-sulfonylimines regio- and stereoselectively, and the resultant palladium(II) species undergo a cascade Suzuki reaction with organoboronic reagents. The substrate scope is substantial for the asymmetric three-component process, and the enantioenriched all-carbon tetra-substituted alkene derivatives are efficiently constructed in a modular and cis-difunctionalized manner. Control experiments and density functional theory (DFT) calculations support the idea that the palladium(0) acts as a π-Lewis base catalyst by chemoselectively forming η2-complexes with the alkene moiety of 1,3-enynes, thus increasing the nucleophilicity of the alkyne group based on the principle of vinylogy, to attack imines enantioselectively. The preferable formation of aza-palladacyclopentene intermediates, via a 90° single bond rotation from the resultant π-allyl complex, guarantees the formal cis-carbopalladation of alkyne group. In addition, a palladium(0)-catalyzed enantioselective reductive coupling of 1,3-enyne and imine is realized by using formic acid as hydrogen transfer reagent.