Divergent projections of the prelimbic cortex mediate autism- and anxiety-like behaviors.

The comorbidity of autism spectrum disorder and anxiety is common, but the underlying circuitry is poorly understood. Here, Tmem74-/- mice showed autism- and anxiety-like behaviors along with increased excitability of pyramidal neurons (PNs) in the prelimbic cortex (PL), which were reversed by Tmem74 re-expression and chemogenetic inhibition in PNs of the PL. To determine the underlying circuitry, we performed conditional deletion of Tmem74 in the PNs of PL of mice, and we found that alterations in the PL projections to fast-spiking interneurons (FSIs) in the dorsal striatum (dSTR) (PLPNs-dSTRFSIs) mediated the hyperexcitability of FSIs and autism-like behaviors and that alterations in the PL projections to the PNs of the basolateral amygdaloid nucleus (BLA) (PLPNs-BLAPNs) mediated the hyperexcitability of PNs and anxiety-like behaviors. However, the two populations of PNs in the PL had different spatial locations, optogenetic manipulations revealed that alterations in the activity in the PL-dSTR or PL-BLA circuits led to autism- or anxiety-like behaviors, respectively. Collectively, these findings highlight that the hyperactivity of the two populations of PNs in the PL mediates autism and anxiety comorbidity through the PL-dSTR and PL-BLA circuits, which may lead to the development of new therapeutics for the autism and anxiety comorbidity.

Zwitterionic Aqua Palladacycles with Noncovalent Interactions for meta-Selective Suzuki Coupling of 3,4-Dichlorophenol and 3,4-Dichlorobenzyl Alcohol in Water.

The site-selective reaction of substrates with multiple reactive sites has been a focus of the current synthetic chemistry. The use of attractive noncovalent interactions between the catalyst and substrate is emerging as a versatile approach to address site-selectivity challenges. Herein, we designed and synthesized a series of palladacycles, to control meta-selective Suzuki coupling of 3,4-dichlorophenol and 3,4-dichlorobenzyl alcohol. Noncovalent interactions directed zwitterionic aqua palladacycles catalyzed meta-selective Suzuki couplings of 3,4-dichloroarenes bearing hydroxyl in water have been developed. Experiments and density functional theory (DFT) calculations demonstrated that the electrostatic interactions play a critical role in meta-selective coupling of 3,4-dichlorophenol, while meta-selective coupling of 3,4-dichlorobenzyl alcohol arises due to the hydrogen-bonding interactions.

Asymmetric Synthesis of Spiropyrazolone-Fused Dihydrofuran-naphthoquinones Bearing Contiguous Stereocenters via a Michael Addition/Chlorination/Nucleophilic Substitution Sequence.

An enantioselective synthesis of spiropyrazolone-fused dihydrofuran-naphthoquinones is first demonstrated via a Michael addition/Chlorination/Nucleophilic substitution sequence. The reactions of 2-hydroxy-1,4-naphthoquinone and α,ß-unsaturated pyrazolones in the presence of the cinchona alkaloid derived hydrogen-bonding catalyst and NCS provide spiropyrazolone-fused 2,3-dihydronaphtho[2,3-b]furan-4,9-diones bearing contiguous stereocenters, of which one is the spiro quaternary stereocenter in high yields with exclusive diastereoselectivity and good to excellent enantioselectivities.

New small-molecule alcohol synthesis by breaking the space limitation of the "aromatic cage" in Pseudomonas sp. AK1 BBOX.

Fe(II)/2OG-dependent oxygenase γ-butyrobetaine hydroxylase (BBOX) stereoselectively hydroxylates inactive C-H bonds and produces L-carnitine. It has potential applications in the biosynthesis of L-carnitine and the synthesis of other small molecule alcohols. In this paper, we systematically explore the substrate range of Pseudomonas sp. AK1 BBOX (psBBOX), with emphasis on the quaternary ammonium portion of γ-butyrobetaine (γ-BB). The space limitation of the "aromatic cage" in psBBOX in the hydroxylation of large quaternary ammonium analogues was studied, and the role of four aromatic amino acid residues in the substrate binding mode was analyzed. Consequently, the F188A mutant was developed with the ability to hydroxylate cyclic quaternary ammonium analogues and generate new alcohol compounds by breaking the limitation of the "aromatic cage".

Anthracite Releases Aromatic Carbons and Reacts with Chlorine to Form Disinfection Byproducts in Drinking Water Production.

Anthracite is globally used as a filter material for water purification. Herein, it was found that up to 15 disinfection byproducts (DBPs) were formed in the chlorination of anthracite-filtered pure water, while the levels of DBPs were below the detection limit in the chlorination of zeolite-, quartz sand-, and porcelain sandstone-filtered pure water. In new-anthracite-filtered water, the levels of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), and ammonia nitrogen (NH3-N) ranged from 266.3 to 305.4 µg/L, 37 to 61 µg/L, and 8.6 to 17.1 µg/L, respectively. In aged anthracite (collected from a filter at a DWTP after one year of operation) filtered water, the levels of the above substances ranged from 475.1 to 597.5 µg/L, 62.1 to 125.6 µg/L, and 14 to 28.9 µg/L, respectively. Anthracite would release dissolved substances into filtered water, and aged anthracite releases more substances than new anthracite. The released organics were partly (around 5%) composed by the µg/L level of toxic and carcinogenic aromatic carbons including pyridine, paraxylene, benzene, naphthalene, and phenanthrene, while over 95% of the released organics could not be identified. Organic carbon may be torn off from the carbon skeleton structure of anthracite due to hydrodynamic force in the water filtration process.

Redox- and pH-Responsive Water-Soluble Flexible Organic Frameworks Realize Synergistic Tumor Photodynamic and Chemotherapeutic Therapy.

Water-soluble 3D polymers with inherent nanoscale pores have been shown to be ideal platforms for the inclusion and delivery of drugs and hold a great promise as biocompatible materials for diagnostic and therapeutic purposes. Herein, a low cytotoxic water-soluble flexible organic framework FOF-S6 with a hydrodynamic diameter of about 127.5 nm is synthesized through the formation of a hydrazone bond from a semirigid tetraaldehyde and a flexible biacylhydrazines which contains a disulfide bond (1:2). FOF-S6 has the ability to dissociate and release inclusion complexes in response to weakly acidic media and glutathione (GSH) overexpressed in tumor cells. More importantly, a facile strategy is developed to contain and deliver aggregation-induced emission photosensitizers (AIE PS, TBD-DQA-540) and chemotherapeutic drugs (Doxorubicin hydrochloride, DOX). DOX-PS@FOF-S6 is synthesized by a one-pot method, which can realize efficient photo-chemotherapy under the guidance of fluorescence imaging, thereby improving the multidrug resistance of tumor cells and the instability of photosensitizers, so as to improve the tumor treatment efficacy.

Routine gastric suspension technique in single-port sleeve gastrectomy procedure.

BACKGROUND: Due to limited technical demand, single-port sleeve gastrectomy (SPSG) is a feasible laparoscopic technique for sleeve gastrectomy (SG). Nonetheless, difficulties exist when performing the single-port technique, and in this study, we aim to describe a slight maneuver that can improve the SPSG procedure. METHODS: Patients who underwent laparoscopic SG between January 2022 and May 2023 at our hospital were included. The patients were classified into two groups: (1) SPSG and (2) multiple-port SG (MPSG). The parameters for this analysis were the patients' age, gender, weight, body mass index (BMI), conversion rate, drainage placement, 30-day readmission rate, and postoperative complications. Postoperative one-month and three-month percentages of total weight loss (%TWL) were calculated and compared. RESULTS: 171 patients were included in this study: (1) the SPSG group (n = 96) and (2) the MPSG group (n = 75). No statistically significant difference was observed within the preoperative (age, gender, height, weight, and BMI) and the perioperative parameters between SPSG and MPSG (operation time, drainage placement, 30-day readmission) (p > 0.05). Per Clavien-Dindo's grading, two patients in the SPSG group suffered grade 1 complications; for the MPSG group, one patient sustained grade 2 and another suffered grade 3b complication. No statistical significance was observed on the %TWL between the two groups (p > 0.05). CONCLUSION: Our study found that performing SPSG in specific patient is feasible and non-inferior when compared to the MPSG. Further studies will be needed to elucidate better the efficacy and safety of performing SPSG.

Synthetic Versus Biological Mesh in Ventral Hernia Repair and Abdominal Wall Reconstruction: A Systematic Review and Recommendations from Evidence-Based Medicine.

AIM: To compare the efficacy and safety of synthetic and biological meshes in ventral hernia repair (VHR) and abdominal wall reconstruction (AWR). METHODS: We screened all clinical trials that reported the application of synthetic and biological meshes in VHR and AWR using Medline, Web of Science, and Embase (Ovid). Only comparative studies with similar baselines such as age, sex, body mass index, degree of wound contamination, and hernia defects between the intervention and control groups were included. Effect sizes with 95% confidence were pooled using a random- or fixed-effects model based on the size of heterogeneity. A sensitivity analysis was performed to test the stability of the results. RESULTS: Ten studies with 1305 participants were included. Biological meshes were associated with significantly higher recurrence rate (OR, 2.09; 95% CI 1.42-3.08; I2 = 50%), surgical site infection (OR, 1.47; 95% CI 1.10-1.97; I2 = 30%), higher re-admission rate (OR, 1.51; 95% CI 1.05-2.17; I2 = 50%), and longer length of hospital stay (SMD, 0.37; 95% CI 0.10-0.65; I2 = 72%). Similar surgical site occurrence, re-operation rate, and mesh explantation rate were observed among biological and synthetic meshes. Biological meshes have no difference in recurrence rate as compared to synthetic meshes, between the clean-contaminated, and contamination-infected fields (OR, 1.41; 95% CI 0.41-4.87 vs 3.00; 95% CI 1.07-8.46; P = 0.36). CONCLUSION: Synthetic meshes are a safe alternative to biological meshes for VHR and AWR. Considering the high cost of biological meshes, synthetic meshes are more appropriate for the VHR and AWR.

Enzymatic deamination of the epigenetic nucleoside N6-methyladenosine regulates gene expression.

N6-methyladenosine (m6A) modification is the most extensively studied epigenetic modification due to its crucial role in regulating an array of biological processes. Herein, Bsu06560, formerly annotated as an adenine deaminase derived from Bacillus subtilis 168, was recognized as the first enzyme capable of metabolizing the epigenetic nucleoside N6-methyladenosine. A model of Bsu06560 was constructed, and several critical residues were putatively identified via mutational screening. Two mutants, F91L and Q150W, provided a superiorly enhanced conversion ratio of adenosine and N6-methyladenosine. The CRISPR-Cas9 system generated Bsu06560-knockout, F91L, and Q150W mutations from the B. subtilis 168 genome. Transcriptional profiling revealed a higher global gene expression level in BS-F91L and BS-Q150W strains with enhanced N6-methyladenosine deaminase activity. The differentially expressed genes were categorized using GO, COG, KEGG and verified through RT-qPCR. This study assessed the crucial roles of Bsu06560 in regulating adenosine and N6-methyladenosine metabolism, which influence a myriad of biological processes. This is the first systematic research to identify and functionally annotate an enzyme capable of metabolizing N6-methyladenosine and highlight its significant roles in regulation of bacterial metabolism. Besides, this study provides a novel method for controlling gene expression through the mutations of critical residues.

Rhodium-Catalyzed Enantioselective 1,4-Oxyamination of Conjugated gem-Difluorodienes via Coupling with Carboxylic Acids and Dioxazolones.

The incorporation of fluorine atoms in organics improves their bioactivity and lipophilicity. Catalytic functionalization of gem-difluorodienes represents one of the most straightforward approaches to access fluorinated alkenes. In contrast to the regular 1,3-dienes that undergo diverse asymmetric di/hydrofunctionalizations, the regio- and enantioselective oxyamination of gem-difluorodienes remains untouched. Herein, we report asymmetric 1,4-oxyamination of gem-difluorodiene by chiral rhodium-catalyzed three-component coupling with readily available carboxylic acid and dioxazolone, affording gem-difluorinated 1,4-amino alcohol derivatives. Our asymmetric protocol exhibits high 1,4-regio- and enantioselectivity with utility in the late-stage modification of pharmaceuticals and natural products. Stoichiometric experiments provide evidences for the π-allylrhodium pathway. Related oxyamination was also realized when trifluoroethanol was used as an oxygen nucleophile.

Correspondence on "Structural Insight into the Catalytic Mechanism of the Endoperoxide Synthase FtmOx1".

In their recent Angewandte Chemie publication (doi: 10.1002/anie.202112063), Cen, Wang, Zhou et al. reported the crystal structure of a ternary complex of the non-heme iron endoperoxidase FtmOx1 (PDB entry 7ETK). The biochemical data assessed in this study were from a retracted study (doi: 10.1038/nature15519) by Zhang, Liu, Zhang et al.; no additional biochemical data were included, yet there was no discussion on the source of the biochemical data in the report by Cen, Wang, Zhou et al. Based on this new crystal structure and subsequent QM/MM-MD calculations, Cen, Wang, Zhou et al. concluded that their work provided evidence supporting the CarC-like mechanistic model for FtmOx1 catalysis. However, the authors did not accurately describe either the CarC-like model or the COX-like model, and they did not address the differences between them. Further, and contrary to their interpretations in the manuscript, the authors' data are consistent with the COX-like model once the details of the CarC-like and COX-like models have been carefully analyzed.

HFIP as Protonation Reagent and Solvent for Regioselective Alkylation of Indoles with All-Carbon Centers.

The regio- and chemoselective construction of indole bearing an all-carbon center at the C3-position, a versatile bioactive building block, by C(sp2)-C(sp3) formation with olefins has been achieved through utilization of hexafluoroisopropanol (HFIP) as the protonation reagent and solvent. The catalytic reactions are operationally simple and green compared with previous reports utilizing elaborated olefins and catalysts. This protocol allows for alkylation of a variety of substituted indoles with diverse of styrene type alkenes in excellent yields and with high selectivity. Application of this protocol to the synthesis of drug was pursued and with an improved yield in contrast to previous art. Catalytic kinetics and deuterium-labeling experiments suggest that the rate-determining step involves the protonation of olefin by HFIP to generate carbocation, followed by electrophilic addition to indole derivative.

Light-Promoted Low-Valent-Tungsten-Catalyzed Ambient Temperature Amination of Boronic Acids with Nitroaromatics.

Triggering C-N bond formation with nitroaromatics and boronic acids at mild conditions is highly desirable, since most prior works were carried out under harsh conditions and sometimes suffered from poor chemo- or regioselectivity. Herein, a low-valent-tungsten-catalyzed reaction that enables the ambient temperature amination of boronic acids with nitroaromatics is disclosed. With readily available W(CO)6 as a precatalyst under external-photosensitizer-free conditions, nitroaromatics smoothly undergo C-N coupling reactions with their boronic acid partners, delivering structurally diverse secondary amines in good yields (>50 examples, yields up to 96%). This methodology is both scalable and highly chemoselective and engages both aliphatic and aromatic boronic acid partners. The catalysis is initiated by the deoxygenation of nitroaromatics by a trans-[W(CO)4(PPh3)2] (trans-W, PPh3 = triphenylphosphine) complex, which forms in situ via ligand replacement.

Fluorescent dyes with multiple quaternary ammonium centers for specific image discrimination and Gram-positive antibacterial activity.

Three quaternary ammonium compounds (QACs), TPQA, T2PQA, and T3PQA, were synthesized and employed in antimicrobial tests against E. coli and S. aureus. It was confirmed that they exhibit selective bacteriostasis against S. aureus. The antibacterial activities of the compounds were evaluated via determining their minimum inhibitory concentrations (MICs) and minimal bactericidal concentrations (MBCs) against S. aureus using the 2,3,5-triphenyltetrazolium chloride (TTC) coloration method. Notably, T2PQA exhibited far better properties than TPQA and T3PQA, with the activity found to be dependent on the structure of the QA and the exposed hydrophobic groups. All three compounds showed promising potential for killing Gram-positive bacteria, efficiently guided by fluorescence imaging.

Occurrence of Iodophenols in Aquatic Environments and the Deiodination of Organic Iodine with Ferrate(VI).

Toxic and odorous iodophenols are commonly identified as disinfection by-products (DBPs) in drinking water. Herein, ng/L levels of iodophenols were identified in river water, wastewater treatment plant effluent, and medical wastewater, with the simultaneous identification of µg/L to mg/L levels of iodide (I-) and total organic iodine (TOI). Oxidation experiment suggested that the I-, TOI, and iodophenols could be oxidized by ferrate [Fe(VI)], and more than 97% of TOI had been transformed into stable and nontoxic IO3-. Fe(VI) initially cleaved the C-I bond of iodophenols and led to the deiodination of iodophenols. The resulted I- was swiftly oxidized into HOI and IO3-, with the intermediate phenolic products be further oxidized into lower molecular weight products. The Gibbs free energy change (ΔG) of the overall reaction was negative, indicating that the deiodination of iodophenols by Fe(VI) was spontaneous. In the disinfection of iodine-containing river water, ng/L levels of iodophenols and chloro-iodophenols formed in the reaction with NaClO/NH2Cl, while Fe(VI) preoxidation was effective for inhibiting the formation of iodinated DBPs. Fe(VI) exhibited multiple functions for oxidizing organic iodine, abating their acute toxicity/cytotoxicity and controlling the formation of iodinated DBPs for the treatment of iodide/organic iodine-containing waters.

First Report of Leaf Spot on Panax notoginseng Caused by Caryophylloseptoria pseudolychnidis in Yunnan, China.

Panax notoginseng is a unique traditional medicinal plant in China, which has the effects of improving myocardial ischemia, protecting liver and preventing cardiovascular diseases (Jiang, 2020). In July 2021, gray-brown round spots were found on the leaves of P. notoginseng in the plantations of Lincang City (23º43´10˝N, 100º7´32˝E). By September, the symptoms were observed on more P. notoginseng plants, with incidence reaching 31%. Initial symptoms on leaves were small, brown spots that expanded, with black granular bulges on the lesions, often surrounded with yellow halo. As the disease progressed, multiple lesions merged, leaves became yellow, and abscission occurred. To isolate the causal pathogen, twelve symptomatic leaves were randomly obtained from twelve P. notoginseng plants. Small pieces of infected leaf tissues (about 5 mm2) were disinfected with 75% ethanol for 30 s, soaked in 2% sodium hypochlorite for 3 min, and then rinsed 3 times with sterile water and blotted dry. Sample tissues were plated on potato dextrose agar (PDA) plates incubated at 25℃ for 5 days with 12 h light/dark photoperiod. Hyphal-tips from the growing edge of colonies were transferred to fresh PDA to obtain pure cultures. Eight isolates were obtained with similar colony morphology, gray (top view) or black (back view) coloration, with a villous surface, and slow-growing on PDA. Conidia were hyaline, slender and obtuse to subobtuse at both ends, 10.3 to 52.62 (av. 25.2) µm × 1.4 to 4.0 (av. 2.4) µm (n=200) in size. Characteristics of the colonies and conidia were consistent with Caryophylloseptoria pseudolychnidis as described by Quaedvlieg et al. (2013) and Verkley et al. (2013). Genomic DNA of three representative isolates (LINC-4 to LINC-6) was extracted, and the rDNA-ITS region, ACT, and LSU gene regions were amplified and sequenced using the primer pairs ITS4/ITS5, 512F/783R, and LSU1Fd/LR5, respectively. Sequences have been deposited in GenBank (OK614104-OK614106 for ITS, OK614109-OK614111 for LSU, OK628350-OK628352 for ACT). BLAST search showed that all sequences were 98% to 100% homology with the corresponding sequences of C. pseudolychnidis. ITS sequences of the three isolates (LINC-4 to LINC-6) showed 99.21% identity (500/504 bp) to C. pseudolychnidis strain CBS 128630 (GenBank accession no. NR156266). LSU sequences of the three isolates showed 99.76% identity (823/825 bp) to C. pseudolychnidis strain CBS 128630 (MH876481). For ACT sequences, LINC-4 and LINC-5 showed 98.53% identity (201/204 bp) to C. pseudolychnidis strain 128614 (KF253599); LINC-6 showed 99.02% identity (202/204 bp) to C. pseudolychnidis strain 128614 (KF253599). Further, the neighbor-joining and maximum-likelihood method were used for multilocus phylogenetic analysis of the obtained sequences using MEGA-X (Kumar et al. 2018). The three isolates were clustered in the same clade with two C. pesudolychidis from database. Three isolates (LINC-4 to LINC-6) were tested for pathogenicity to confirm Koch's postulates. Annual potted P. notoginseng was inoculated with spore suspension (105 spores.mL-1). Each isolate was inoculated onto two leaves each of five P. notoginseng plants. The controls were similarly mock-inoculated with sterile water. To maintain high humidity (>90% RH), all plants were placed in transparent plastic boxes in a greenhouse at 25℃ with a 12 h light/dark photoperiod. Fifteen days post-inoculation, inoculated leaves showed similar symptoms to those observed in the field, and control plants remained healthy. The pathogen were reisolated from symptomatic leaf spots, and the colony characteristics were the same as those of the original isolates. Morphological characteristics, molecular data, and Koch's postulates tests confirmed C. pseudolychnidis as the cause of P. notoginseng leaf spot disease. To our knowledge, this is the first report of C. pseudolychnidis causing leaf spot on P. notoginseng in Yunnan, China. The spread of this disease might pose a serious threat to the production of P. notoginseng. The occurrence and spread of this pathogen should be further studied in order to formulate reasonable control measures.

In-situ electrodeposition synthesis of Z-scheme rGO/g-C3N4/TNAs photoelectrodes and its degradation mechanism for oxytetracycline in dual-chamber photoelectrocatalytic system.

The dual-chamber photoelectrocatalytic (PEC) system possess advantages in the degradation efficiency and processing cost of organic contaminants. In this study, TiO2 nanotube arrays modified by rGO and g-C3N4 (rGO/g-C3N4/TNAs) photoelectrodes were successfully prepared. The surface micromorphology, chemical structure, crystal structure, and basic element composition of rGO/g-C3N4/TNAs photoelectrodes were studied by SEM, FTIR, XRD, Raman, and XPS. UV-vis absorption, photoluminescence (PL) spectra, and photoelectrochemical (PECH) tests were used to explore the photoelectrochemical characteristics of rGO/g-C3N4/TNAs photoelectrodes. Under simulated sunlight illumination, the dual-chamber PEC system with external bias voltage was used to investigate the degradation of oxytetracycline (OTC) on rGO/g-C3N4/TNAs photoelectrodes. The results showed that rGO and g-C3N4 were successfully loaded on TNAs, and the separation efficiency of electrons and holes at rGO/g-C3N4/TNAs photoelectrodes was improved. The light absorption range of rGO/g-C3N4/TNAs photoelectrodes extends to the visible light region and has better light absorption performance. Compared with the photocatalytic process, when 1.2 V bias voltage was applied, the degradation efficiency of OTC in anode and cathode chambers in PEC were increased by 3.28% and 44.01% within 60 min, respectively. In addition, the anode and cathode chambers have different degradation effects on OTC. Both the external bias voltage and initial pH have significant effects in cathode chamber, but have little effect in photoanode chamber. The fluorescence excitation-emission matrix spectra and liquid chromatography-tandem mass spectrometry showed that there were different intermediates in the degradation process of OTC. This study indicated that for the dual-chamber PEC system, rGO/g-C3N4/TNAs photoelectrodes exhibited excellent photocatalytic performance and have potential application prospects in water environmental remediation.

Metallo-Supramolecular Octahedral Cages with Three Types of Chirality towards Spontaneous Resolution.

Chirality is one of the most important intrinsic properties of (supra)molecules. In this study, we obtained enantiomeric metallo-supramolecular octahedra without using any chiral sources. Such cages were self-assembled by prochiral trispyridine ligand L based on a C3h truxene core and CuII salts. Crystallization of the cages with BF4 - as counterions afforded racemate crystals; while crystallizations of cages with ClO4 - and OTf- as counterions resulted in conglomerates with spontaneous resolution. Three types of chirality were observed in each cage, including planar chirality of the truxene core, axial chirality from the pyridyl and truxene moieties, and propeller chirality of the pyridyl-CuII coordination sites. The cages reported here are among the largest discrete synthetic metallo-supramolecules ever reported with chiral self-sorting behavior. Remarkably, the chiral cages exhibited very slow racemization even at low concentrations, suggesting their high stability in solution.

Iron-Catalyzed Regiodivergent Hydrostannation of Alkynes: Intermediacy of Fe(IV)-H versus Fe(II)-Vinylidene.

We report an iron system, Cp*Fe(1,2-R2PC6H4X), which controls the Markovnikov and anti-Markovnikov hydrostannation of alkynes by tuning the ionic metal-heteroatom bonds (Fe-X) reactivity. The sequential addition of nBu3SnH to the iron-amido catalyst (1, X = HN-, R = Ph) affords a distannyl Fe(IV)-H species responsible for syn-addition of the Sn-H bond across the C≡C bond to produce branched α-vinylstannanes. Activation of the C(sp)-H bond of alkynes by an iron-aryloxide catalyst (2, X = O-, R = Cy) affords an iron(II) vinylidene intermediate, allowing for gem-addition of the Sn-H to the terminal-carbon producing ß-vinylstannanes. These catalytic reactions exhibit excellent regioselectivity and broad functional group compatibility and enable the large-scale synthesis of diverse vinylstannanes. Many new reactions have been established based on such a synthetic Fe-X platform to demonstrate that the initial step of the catalysis is conveniently controlled by the activation of either the tin hydride or the alkyne substrate.