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The Michael‐type addition of indoles represents one of the most important C−C bonds forming reactions at their C‐3 position. Herein, we present a mild, versatile and sustainable protocol for the efficient preparation of β‐indolylketones via a Michael addition between indoles and chalcones or α,β‐unsaturated ketones in the presence of substituted arylazo sulfones as photoacid generators (PAGs). [ABSTRACT FROM AUTHOR]

Background: Ischemic stroke belongs to "apoplexy" and its pathogenesis is characterized by qi deficiency and blood stasis combining with phlegm-damp clouding orifices. Buqi-Huoxue-Tongnao decoction (BHTD) is a traditional Chinese medicine formula for qi deficiency, blood stasis and phlegm obstruction syndrome. However, its efficacy and potential mechanism on ischemic stroke are still unclear. This study aims to investigate the protective effect and potential mechanism of BHTD against ischemic stroke. Materials and methods: Middle cerebral artery occlusion (MCAO) surgery was carried out to establish an ischemic stroke model in rats. Subsequently, the rats were gavaged with different doses of BHTD (2.59, 5.175, 10.35 g/kg) for 14 days. The protective effects of BHTD on the brain and gut were evaluated by neurological function scores, cerebral infarction area, levels of brain injury markers (S-100B, NGB), indicators of gut permeability (FD-4) and bacterial translocation (DAO, LPS, D-lactate), and tight junction proteins (Occludin, Claudin-1, ZO-1) in brain and colon. 16S rRNA gene sequencing and metabolomic analysis were utilized to analyze the effects on gut microecology and screen for marker metabolites to explore potential mechanisms of BHTD protection against ischemic stroke. Results: BHTD could effectively mitigate brain impairment, including reducing neurological damage, decreasing cerebral infarction and repairing the blood–brain barrier, and BHTD showed the best effect at the dose of 10.35 g/kg. Moreover, BHTD reversed gut injury induced by ischemic stroke, as evidenced by decreased intestinal permeability, reduced intestinal bacterial translocation, and enhanced intestinal barrier integrity. In addition, BHTD rescued gut microbiota dysbiosis by increasing the abundance of beneficial bacteria, including Turicibacter and Faecalibaculum. Transplantation of the gut microbiota remodeled by BHTD into ischemic stroke rats recapitulated the protective effects of BHTD. Especially, BHTD upregulated tryptophan metabolism, which promoted gut microbiota to produce more indole lactic acid (ILA). Notably, supplementation with ILA by gavage could alleviate stroke injury, which suggested that driving the production of ILA in the gut might be a novel treatment for ischemic stroke. Conclusion: BHTD could increase gut microbiota-derived indole lactic acid to attenuate ischemic stroke via the gut-brain axis. Our current finding provides evidence that traditional Chinese medicine can ameliorate central diseases through regulating the gut microbiology. [ABSTRACT FROM AUTHOR]

Various indoles undergo Friedel–Crafts alkylation at the 3-position when treated with secondary arylmethyl acetates in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) and 2,6-lutidine. Tertiary benzylic alcohols are also effective alkylating agents, undergoing TMSOTf-promoted activation to yield alkylated indoles that feature quaternary centers. A related study shows that benzofuran reacts under similar conditions to yield 2-alkylated benzofurans when treated with similar alkylating agents, and the reaction has been extended to include other representative heteroarenes. Yields for these Friedel–Crafts alkylation products range from 43%–99% over a wide range of substrate combinations. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Herein, we report rhodium catalyzed N‐arylation via addition of arylboronic acids to electron‐deficient α‐iminoesters which can be prepared in high efficiency by using easily accessible β‐carbonyl esters. The reaction is highly regiospecific to achieve the N‐aryl addition efficiently with up to 99% yield under mild conditions. The corresponding product can be further efficiently converted into indoles and a series of other important building blocks. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: In this paper, the difunctionalizative perfluoroalkyloximation of alkenes has been developed for the first time. This photochemical method allows for the synthesis of various perfluoroalkyl ethanone oximes with excellent regioselectivity and good functional group tolerance. Our method employs the most common perfluoroalkyl source, perfluoroalkyl iodides, as Rf reagents. Besides long‐chain perfluoroalkyl groups, this approach could be extended to incorporating additional groups, including trifluoromethyl, difluoromethyl, sulfonyl, and malonate, selectively into olefins, resulting in a range of β‐substituted ethanone oximes. Notably, the potential of this method in the Fukuyama indole synthesis, generating novel 2‐perfluoroalkylated 3‐(α‐oximidobenzyl)indoles via a radical cascade mechanism with 2‐vinylphenylacryloyl isocyanate as the radical acceptor, presents a compelling avenue for drug synthesis. The protocol is efficient, scalable, and useful for late‐stage modification of bioactive molecules. [ABSTRACT FROM AUTHOR]

The article focuses on recent advancements in chemistry, highlighting the development of new materials and chemical processes. Topics include the synthesis of insensitive energetic materials with enhanced detonation performance, the use of vanadium(V) complexes for syndiospecific ring-opening metathesis polymerization (ROMP) of cyclic olefins, and the exploration of metal-support interactions to enhance catalytic activity for hydrogen production.

The present work involves an improved, pseudo-three-component synthetic approach for the synthesis of dimeric indoles using 4 mol% [BCMIM][Cl] ionic liquid via metal-free synthesis in aqueous ethanol under reflux conditions. A series of 35 derivatives were furnished in up to 95% yields in 0.5 h to 1.5 h. These derivatives were then analyzed using various spectroscopic techniques. The salient features of this methodology are mild reaction conditions, metal-free synthesis, simple work-up procedure, short reaction time, reusability for up to 4 cycles, good to excellent yields and low catalyst loading. The UV-visible and fluorescence spectroscopy techniques were used to investigate the photophysical characteristics of selected derivatives. The absorption and emission spectra reveal a peak wavelength (λmax) in the ranges of 216–228 nm (π–π*), 262–294 nm (n–π*), and 389–407 nm, respectively. A similar trend to the experimental data can be observed in density functional theory (DFT) calculations. The binding affinities of the synthesised derivatives with bovine serum albumin (BSA) and deoxyribonucleic acid (DNA) were computed using AutoDock Vina. Furthermore, 7af, 7ai, 7aj and 7gk were investigated for BSA and DNA binding studies. The ligands exhibited a binding strength of 105 and 103 M−1 with BSA and DNA, respectively. The ethidium bromide (EtBr) displacement assay discloses intercalation as the mode of binding with Ksv values in the order of 102–103 M−1. [ABSTRACT FROM AUTHOR]

Herein, we present an efficient, one‐pot reaction for accessing 3‐benzylated indoles via the coupling of benzyl alcohols with indoles under heterogeneous catalysis by manganese ferrite (MnFe2O4) nanoparticles. Notably, this reaction, for the first time, employs MnFe2O4 nanoparticles prepared using a simple grinding method. The high compatibility of MnFe2O4 nanoparticles enables a broad substrate scope and high regioselectivity. Moreover, this approach offers several attractive highlights including the use of a recyclable oxide catalyst and green and cost‐effective alkylating reagents under solvent‐free conditions. [ABSTRACT FROM AUTHOR]

A series of novel 2‐(chloromethyl)‐5‐(3, 5‐disubstituted‐1H‐indol‐2‐yl)‐1,3,4‐oxadiazole (3 a–h) derivatives have been synthesized as potential COX inhibitors, anti‐TB, and anti‐oxidant activities. The structures were confirmed by IR, NMR (1H and 13C) mass spectral techniques. The physicochemical properties, ADME, and drug‐likeness profile for the synthesized compounds were evaluated by SwissADME. Based on our interest in indole chemistry and SAR study, foresaid indole compounds were examined for in vitro COX inhibitory activity, anti‐TB, and antioxidant activities. The physicochemical and ADME studies were disclosed for newly synthesized compounds. The compounds 3 a,3 b and 3 c recognized outstanding COX‐II inhibitions with IC50 values of 0.28, 0.24, and 0.45 μM compared to standard drugs. The compounds 3 a,and3 b showed outstanding anti‐TB activity with MIC value 0.78 μg/mL. The compounds 3 a,3 b, and 3 c attested outstanding antioxidant activity at 10 μg/ml with a rate of inhibition of 66.52 %, 68.25 %, and 65.95 % respectively. Finally, the molecular docking studies carried out with cyclooxygenase‐2 (PDB ID: 6COX), M. tuberculosis enoyl reductase (INHA) complexed with 1‐cyclohexyl‐N‐(3,5‐dichlorophenyl)‐5‐oxopyrrolidine‐3‐carboxamide (PDB ID: 4TZK), and cytochrome c peroxidase (PDB ID: 2X08), for all the newly synthesized derivatives. Finally, selected compounds were taken for their molecular dynamic studies. [ABSTRACT FROM AUTHOR]

Pyrroles and indoles bearing N‐allenyl tethers participate in a variety of iridium‐catalyzed cycloisomerization processes initiated by a C−H activation step, to deliver a diversity of synthetically relevant azaheterocyclic products. By appropriate selection of the ancillary ligand and the substitution pattern of the allene, the reactions can diverge from simple intramolecular hydrocarbonations to tandem processes involving intriguing mechanistic issues. Accordingly, a wide range of heterocyclic structures ranging from dihydro‐indolizines and pyridoindoles to tetrahydroindolizines, as well as cyclopropane‐fused tetrahydroindolizines can be obtained. Moreover, by using chiral ligands, these cascade processes can be carried out in an enantioselective manner. DFT studies provide insights into the underlying mechanisms and justify the observed chemo‐ regio‐ and stereoselectivities. [ABSTRACT FROM AUTHOR]

Lamellarins are natural products with a [3,4]-fused pyrrolocoumarin skeleton possessing interesting biological properties. More than 70 members have been isolated from diverse marine organisms, such as sponges, ascidians, mollusks, and tunicates. There is a continuous interest in the synthesis of these compounds. In this review, the synthetic strategies for the synthesis of the title compounds are presented along with their biological properties. Three routes are followed for the synthesis of lamellarins. Initially, pyrrole derivatives are the starting or intermediate compounds, and then they are fused to isoquinoline or a coumarin moiety. Second, isoquinoline is the starting compound fused to an indole moiety. In the last route, coumarins are the starting compounds, which are fused to a pyrrole moiety and an isoquinoline scaffold. The synthesis of isolamellarins, azacoumestans, isoazacoumestans, and analogues is also described. The above synthesis is achieved via metal-catalyzed cross-coupling, [3 + 2] cycloaddition, substitution, and lactonization reactions. The title compounds exhibit cytotoxic, multidrug resistance (MDR), topoisomerase I-targeted antitumor, anti-HIV, antiproliferative, anti-neurodegenerative disease, and anti-inflammatory activities. [ABSTRACT FROM AUTHOR]

Simple Summary: Sentinel lymph node (SLN) mapping is a crucial technique in the surgical treatment of cervical cancer, helping to identify the first lymph nodes that cancer may spread to. Indocyanine green (ICG) is a dye commonly used to make these lymph nodes visible during surgery, but there is no agreement on the best amount to use. This research reviews different amounts of ICG used in previous studies to determine the most effective dose for detecting these lymph nodes. By identifying the best practices, this study aims to improve the accuracy and safety of surgeries for cervical cancer patients. The findings could help standardize the use of ICG in clinical practice, leading to better outcomes for patients and providing clearer guidelines for surgeons. Over the past decade, SLN mapping has become increasingly important in cervical cancer surgery. ICG is the most commonly used tracer due to its high bilateral detection rates, ease of use, and safety. However, there is no consensus on the optimal ICG dose, leading to variability in outcomes. This systematic review aims to evaluate the impact of different ICG doses on SLN detection in early-stage cervical cancer, identifying the most effective and safe dose for clinical practice. A comprehensive search was conducted in MEDLINE/PubMed up to May 2024. Studies included assessed SLN mapping using ICG in stage IA2-IIA/IIB cervical cancer. Exclusions were applied to studies not reporting ICG dose or using multiple tracers without dose-specific results. Twelve studies were included, with ICG concentrations ranging from 0.25 mg/mL to 25 mg/mL and injection volumes from 1 to 10 mL. Overall SLN detection rates ranged from 88% to 100%, while bilateral detection rates varied between 74.1% and 98.5%. The most consistent results were obtained with an ICG concentration of 1.25 mg/mL and a 4 mL injection volume. In conclusion, an ICG concentration of 1.25 mg/mL with a 4 mL injection volume is recommended for effective SLN mapping in cervical cancer, achieving high detection rates with minimal variability. Standardizing this dose in clinical practice is suggested to improve reproducibility and outcomes. [ABSTRACT FROM AUTHOR]

Marine sponges harbor diverse secondary metabolites with a variety of biological activity, many of which are considered as chemical defense substances for the sponges themselves. Recently, we observed that Thromidia catalai, one of the largest species of starfish, feeds on the sponge Theonella swinhoei (chemotype Y), known to contain diverse biologically active metabolites. Here we report the isolation of three novel brominated indole alkaloids, catalindoles A–C, from the arms of T. catalai as well as the elucidation of their structures. Their structures were determined by a combination of spectroscopic data analyses and chemical methods, and they were further confirmed by chemical syntheses of the molecules. Moreover, we revealed the predator–prey relationship between T. catalai and Theonella sponges in terms of chemical components, noting that T. catalai feeds not only on T. swinhoei (chemotype Y) but also on T. swinhoei (chemotype W). [ABSTRACT FROM AUTHOR]

Sulfenyl indole moieties, in particular, 2 or 3-substituted Sulfenyl indoles are prevalent in diverse natural products, biologically active compounds, and pharmaceuticals, which are required for curing many diseases, such as virology, cancers, HIV, allergies, respiratory disorders, etc. Owing to their prevalence in natural and synthesized functional organic molecules, indoles keep receiving tremendous attention in the research and application of many disciplines such as chemistry, biology, pharmaceuticals. In this context, our main objective is to synthesize derivatives of 3-Substituted Sulfenyl Indole as Anti-Viral compounds (primarily against DENV). [ABSTRACT FROM AUTHOR]

Background: Hepatic arterial infusion pump (HAIP) treatment is a technique used to treat liver localized malignancy with intra-arterial chemotherapy. Methylene blue is generally administered to verify hepatic perfusion and exclude inadvertent extrahepatic perfusion. The use of indocyanine green dye (ICG) combined with near-infrared (NIR) fluorescence imaging during robot-assisted HAIP placement may be an attractive alternative by providing high contrast without blue discoloration of the operative field. Methods: Data was collected retrospectively from 2 centers in the Netherlands. Intraoperative perfusion of the liver segments and extrahepatic perfusion were assessed using ICG/NIR as well as methylene blue on video imaging and correlated to postoperative 99 m-Tc perfusion scintigraphy. Results: 13 patients underwent robot-assisted surgery for HAIP placement; median length of stay was 4 days, complications occurred in 4 patients. Hepatic perfusion showed identical patterns when ICG was compared with methylene blue. In 1 patient, additional extrahepatic perfusion was found using ICG, leading to further vessel ligation. Intraoperative ICG perfusion was concordant with 99 m-Tc perfusion scintigraphy. Discussion: Liver and extrahepatic perfusion determined by ICG fluorescence imaging is concordant with blue dye perfusion and 99 m-Tc perfusion scintigraphy. Therefore, ICG fluorescence imaging is deemed a safe and reliable technique for perfusion testing during robot-assisted HAIP placement. [ABSTRACT FROM AUTHOR]

A series of 1-carbonyl-1H-indoles were prepared by 2-iodoanilines and calcium carbide in a one-pot reaction catalyzed by recyclable10% Pb/C, resulting in the corresponding substituted indoles in good yields. This protocol offers several advantages, including the utilization of sustainable, low-cost calcium carbide, an easy-to-handle acetylene source, and recyclable Pb/C catalysts. The synthesis of a series of 1-carbonyl-1H-indoles were prepared by 2-iodoanilines and calcium carbide in a one-pot reaction catalyzed by 10% Pb/C, resulting in the corresponding substituted indoles in good yields. This protocol offers several advantages, including the utilization of sustainable, low-cost feedstock, an easy-to-handle acetylene source, and recyclable Pb/C catalysts. [ABSTRACT FROM AUTHOR]

Background The activity of PARP inhibitors (PARPi) in patients with homologous recombination repair (HRR) mutations and metastatic castration-resistant prostate cancer has been established. We hypothesized that the benefit of PARPi can be maintained in the absence of androgen deprivation therapy (ADT) in an HRR-mutated population. We report the results of a phase II clinical trial of rucaparib monotherapy in patients with metastatic hormone-sensitive prostate cancer (mHSPC). Methods This was a multi-center, single-arm phase II trial (NCT03413995) for patients with asymptomatic, mHSPC. Patients were required to have a pathogenic germline mutation in an HRR gene for eligibility. All patients received rucaparib 600 mg by mouth twice daily, without androgen deprivation. The primary endpoint was a confirmed PSA50 response rate. Results Twelve patients were enrolled, 7 with a BRCA1/2 mutation and 5 with a CHEK2 mutation. The confirmed PSA50 response rate to rucaparib was 41.7% (N = 5/12, 95% CI: 15.2-72.3%, one-sided P  = .81 against the 50% null), which did not meet the pre-specified efficacy boundary to enroll additional patients. In patients with measurable disease, the objective response rate was 60% (N = 3/5), all with a BRCA2 mutation. The median radiographic progression-free survival on rucaparib was estimated at 12.0 months (95% CI: 8.0-NR months). The majority of adverse events were grade ≤2, and expected. Conclusion Rucaparib can induce clinical responses in a biomarker-selected metastatic prostate cancer population without concurrent ADT. However, the pre-specified efficacy threshold was not met, and enrolment was truncated. Although durable responses were observed in a subset of patients, further study of PARPi treatment without ADT in mHSPC is unlikely to change clinical practice. [ABSTRACT FROM AUTHOR]

A straightforward one‐pot synthesis method has been developed for combining the vic‐dioxime scaffold with the indole nucleus. Sixteen new mono‐ and bis‐indole dioximes were prepared as the first example of C−C coupling between readily available chloroglyoximes with indoles. This atom‐economic method requires only a stoichiometric amount of inexpensive sodium acetate and does not require any catalysts or toxic solvents. The reaction conditions were optimized and proceeded smoothly under mild conditions, providing good yields of the desired indole dioximes. The structures of synthesized vic‐dioximes were characterized using NMR, FT‐IR, and LC–MS. To shed light on the molecular structure, an extensive series of theoretical computations were performed on a representative molecule (3 a) using the DFT−B3LYP/6‐311++G(d,p) level of theory. The symmetrical and unsymmetrical indole dioximes obtained as key intermediates in this work have the potential to serve as essential building blocks for the design of new nortopsentin analogs with enhanced biological activities. To support this assumption, a representative molecule (3 a) was converted to a novel nortopsentin analog (4 a) having a 1,2,5‐oxadiazole (furazan) ring core. [ABSTRACT FROM AUTHOR]

Fluorine being a magic element and Indole being a magic molecule, their cumulative effect has tremendously increased the potential of resulting moiety for drug development. Keeping this in mind, we are describing a comprehensive account on the recent strategies for the synthesis of trifluoromethylated indoles, indoline and oxindoles. In this review we have explored two types of strategies for trifluoromethylation reactions, one involves direct installation of CF3 group at indole moiety via C−H activation and substitution where as other is by the cyclization reaction of the starting compound containing CF3 group. The reactions were explored for the substrate scope and mechanism using controlled experiments. [ABSTRACT FROM AUTHOR]

A highly enantioselective Pd/Bim-catalyzed dearomative Michael reaction applying polycyclic tropones as non-benzenoid aromatic Michael acceptors and arylboronic acids as aryl pronucleophiles has been developed. The bridged biaryls bearing central and axial chirality, including pentacyclic cyclohepta[b]indoles and 6,7-dihydrodibenzo- [a,c][7]annulen-5-ones, are generally generated in good to high yields and excellent enantioselectivities and can be readily transformed into useful derivatives. [ABSTRACT FROM AUTHOR]

Background: Oxidative stress (OS) is one of the major causes of ovarian aging and dysfunction. Indole-3-propionic acid (IPA) is an indole compound derived from tryptophan with free radical scavenging and antioxidant properties, and thus may have potential applications in protecting ovarian function, although the exact mechanisms are unknown. This study aims to preliminarily elucidate the potential mechanisms of IPA that benefit ovarian reserve function through network pharmacology, molecular docking, and experimental verification. Methods: The related protein targets of IPA were searched on SwissTargetPrediction, TargetNet, BATMAN-TCM, and PharmMapper databases. The potential targets of diminished ovarian reserve (DOR) were identified from OMIM, GeneCards, DrugBank, and DisGeNET databases. The common targets were uploaded directly to the STRING database to construct PPI networks. We then performed GO and KEGG enrichment analysis on the targets. Subsequently, molecular docking and molecular dynamics simulation were used to validate the binding conformation of IPA to candidate targets. Furthermore, we carried out in vitro experiments to validate the prediction results of network pharmacology. Results: We identified a total of 61 potential targets for the interaction of IPA with DOR. The PPI network topological parameter analysis yielded 13 hub genes for DOR treatment. The GO biological process enrichment analysis identified 293 entries, mainly enriched in aging, signal transduction, response to hypoxia, negative regulation of apoptotic process, and positive regulation of cell proliferation. The KEGG enrichment analysis mainly included lipid and atherosclerosis, progesterone-mediated oocyte maturation, AGE-RAGE, relaxin, estrogen, and other signaling pathways. The molecular docking further revealed the direct binding of IPA with six hub proteins including NOS3, AKT1, EGFR, PPARA, SRC, and TNF. In vitro experiments showed that IPA pretreatment attenuated H2O2-induced cellular oxidative stress damage, while IPA exerted cytoprotective and antioxidant damage effects by regulating the six hub genes and antioxidant proteins. Conclusion: We systematically illustrated the potential protective effects of IPA against DOR through multiple targets and pathways using network pharmacology, and further verified the cytoprotective effect and antioxidant properties of IPA through in vitro experiments. These findings provide new insights into the targets and molecular mechanisms whereby IPA improves DOR. [ABSTRACT FROM AUTHOR]

Background: The indocyanine green (ICG) fluorescence test has become a standard test in surgical procedures, facilitating the assessment of blood perfusion in real-time. While its utility in emergency surgeries for evaluating anastomotic blood supply is well-established, its application in trauma cases, especially those involving mesenteric hematoma, remains underexplored. Herein, we present a case to illustrate the efficacy of the ICG fluorescence test in such scenarios. Case presentation: A 51-year-old man with uncontrolled hypertension suffered blunt abdominal trauma following a motor vehicle accident. We used the intra-operative ICG fluorescence test to chart the surgical plan for the patient. A combination of diagnostic laparoscopy with ICG fluorescence testing effectively excluded bowel ischemia, leading to the avoidance of intestinal resection and the need for a temporary ostomy. The patient resumed enteral nutrition. Conclusions: Our case underscores the efficacy of ICG fluorescence testing in assessing bowel viability and guiding surgical strategies in trauma patients with mesenteric hematoma. By facilitating real-time visualization of blood perfusion, ICG testing enables the adoption of conservative treatments in patients who would traditionally require more invasive surgical interventions, with minimal effect on operation time and cost. [ABSTRACT FROM AUTHOR]

An air‐stable, inexpensive, and isolable cobalt(II) complex (C1) of N‐((1‐methyl‐1H‐imidazol‐2‐yl)methyl)‐2‐(phenylselanyl)ethan amine (L1) was synthesized and characterized. The complex was used to catalyze a one‐pot cascade reaction between 2‐(2‐aminophenyl)ethanols and benzyl alcohol derivatives. Interestingly, 2‐aryl‐3‐formylindole derivatives were formed instead of N‐alkylated or C‐3 alkylated indoles. A broad substrate scope can be activated using this protocol with only 5.0 mol % catalyst loading to achieve up to 87 % yield of 2‐aryl‐3‐formylindole derivatives. The mechanistic studies suggested that the reaction proceeds through tandem imine formation followed by cyclization. [ABSTRACT FROM AUTHOR]

An efficient and rapid protocol for the oxidative halogenation of tryptamines with 10 % aqueous NaClO has been developed. This reaction is featured by its operational simplicity, metal‐free conditions, no purification, and high yield. Notably, the resulting key intermediates are suitable for further functionalization with various nucleophiles, including amines, N‐aromatic heterocycles, indoles and phenols. The overall transformation exhibits broad functional‐group tolerance and is applicable to the late‐stage functionalization of complex biorelevant molecules. [ABSTRACT FROM AUTHOR]

The synthesis of indoles with a trifluoromethyl group has attracted a lot of attention because they are promising structural subunits for pharmaceuticals and agrochemicals. As part of our project aimed toward the upcycling of hydrofluoroolefins (HFOs), we developed a method to construct a CF3‐bearing indole ring system through the Suzuki–Miyaura cross‐coupling of a brominated HFO‐1234ze(E) (CF3CH=CHF) with N‐tosylated o‐borylanilines, followed by nucleophilic 5‐endo‐trig cyclization at the vinylic position of the generated fluorostyrenes. We found that the Pd2(dba)3/SPhos catalyst system in the presence of K2CO3 and water in toluene afforded the corresponding 3‐CF3‐indoles in high yields in a one‐pot operation. [ABSTRACT FROM AUTHOR]

The document is the contents list for an issue of the journal Chemical Communications. It includes the titles and authors of various articles and features that will be included in the issue. The articles cover a range of topics in the field of chemistry, including recent advances in biosensing systems, continuous flow synthesis, electrochemical construction, and more. The journal is published by The Royal Society of Chemistry, a leading chemistry community. [Extracted from the article]

Indole motifs are important heterocycles found in natural products, pharmaceuticals, agricultural chemicals, and materials. Although there are well-established classical name reactions for indole synthesis, these transformations often require harsh reaction conditions, have a limited substrate scope, and exhibit poor regioselectivity. As a result, organic synthesis chemists have been exploring efficient and practical methods, leading to numerous strategies for synthesizing a variety of functionalized indoles. In recent years, electrochemistry has emerged as an environmentally friendly and sustainable synthetic tool, with widespread applications in organic synthesis. This technology allows for elegant synthetic routes to be developed for the construction of indoles under external oxidant-free conditions. This feature article specifically focuses on recent advancements in indole synthesis from non-indole-based substrates, as well as the mechanisms underlying these transformations. [ABSTRACT FROM AUTHOR]

An efficient palladium-catalyzed cascade cyclization/carbonylation of indoles with aryl formates to access ester-functionalized indolo[2,1-a]isoquinoline scaffolds has been developed. In addition, an asymmetric variant is also achieved using a chiral phosphine ligand, affording the indolo[2,1-a]isoquinoline products in good yields and enantioselectivities. [ABSTRACT FROM AUTHOR]

An air‐stable, inexpensive, and isolable cobalt(II) complex (C1) of N‐((1‐methyl‐1H‐imidazol‐2‐yl)methyl)‐2‐(phenylselanyl)ethan amine (L1) was synthesized and characterized. The complex was used to catalyze a one‐pot cascade reaction between 2‐(2‐aminophenyl)ethanols and benzyl alcohol derivatives. Interestingly, 2‐aryl‐3‐formylindole derivatives were formed instead of N‐alkylated or C‐3 alkylated indoles. A broad substrate scope can be activated using this protocol with only 5.0 mol % catalyst loading to achieve up to 87 % yield of 2‐aryl‐3‐formylindole derivatives. The mechanistic studies suggested that the reaction proceeds through tandem imine formation followed by cyclization. [ABSTRACT FROM AUTHOR]

A dearomative oxidation of pyrroles to Δ3‐pyrrol‐2‐ones is described, which employs a sulfoxide as oxidant, in conjunction with a carboxylic acid anhydride and a Brønsted acid additive. 3‐substituted pyrroles undergo regioselective oxidation to give the product isomer in which oxygen has been introduced at the more hindered position. Regioselectivity is rationalized by a proposed mechanism that proceeds by initial thianthrenium introduction at the less‐hindered pyrrole α‐position, followed by distal attack of an oxygen nucleophile and subsequent elimination of thianthrene. The same reaction conditions are also able to effect a chemoselective oxidation of indoles to indolin‐3‐ones and additionally of indolin‐3‐ones to 2‐hydroxyindolin‐3‐ones. Here again, the regio‐ and chemoselectivities are rationalized through the intermediacy of a thianthrenium salt. [ABSTRACT FROM AUTHOR]

We describe the first total syntheses of tabernanthine and ibogaline. Entry to these iboga alkaloid natural products is enabled by a thermal coupling of indoles and aziridines to furnish the requisite nosyl tryptamine starting materials. This route features a Friedel‐Crafts type alkylation to form the key indole‐isoquinuclidine C−C bond. Finally, a regio‐ and diastereoselective hydroboration‐oxidation enables C−N bond formation to close the isoquinuclidine ring system and deliver tabernanthine and ibogaline in 10 and 14 % yield respectively. Both syntheses were completed in eight steps. [ABSTRACT FROM AUTHOR]

We herein reported, a visible‐light‐induced K2S2O8 mediated cascade reaction of 3‐(2‐isocyanoethyl)indoles with α‐oxocarboxylic acids leading to diastereoselective synthesis of polycyclic spiroindolines bearing an N‐formyl unit derivative utilising the alkali metal salt K2S2O8 as a mediator under mild reaction conditions. This study offers an illustration of α‐oxocarboxylic acids and 3‐(2‐isocyanoethyl)indoles‐based reactions as it shows the involvement of glyoxolate ions without decarboxylation to access polycyclic spiroindolines bearing an N‐formyl unit analogue. The batch process can be extended to a continuous flow system using a glass tube loaded with K2S2O8 placed between the PFA capillary reactor, which can greatly advance the reaction efficiency and can even be promoted to gram‐scale synthesis. [ABSTRACT FROM AUTHOR]

Background: Preserving sufficient oxygen supply to the tissue is fundamental for maintaining organ function. However, our ability to identify those at risk and promptly recognize tissue hypoperfusion during abdominal surgery is limited. To address this problem, we aimed to develop a new method of perfusion monitoring that can be used during surgical procedures and aid surgeons' decision-making. Methods: In this experimental porcine study, thirteen subjects were randomly assigned one organ of interest [stomach (n = 3), ascending colon (n = 3), rectum (n = 3), and spleen (n = 3)]. After baseline perfusion recordings, using high-frequency, low-dose bolus injections with weight-adjusted (0.008 mg/kg) ICG, organ-supplying arteries were manually and completely occluded leading to hypoperfusion of the target organ. Continuous organ perfusion monitoring was performed throughout the experimental conditions. Results: After manual occlusion of pre-selected organ-supplying arteries, occlusion of the peripheral arterial supply translated in an immediate decrease in oscillation signal in most organs (3/3 ventricle, 3/3 ascending colon, 3/3 rectum, 2/3 spleen). Occlusion of the central arterial supply resulted in a further decrease or complete disappearance of the oscillation curves in the ventricle (3/3), ascending colon (3/3), rectum (3/3), and spleen (1/3). Conclusion: Continuous organ-perfusion monitoring using a high-frequency, low-dose ICG bolus regimen can detect organ hypoperfusion in real-time. [ABSTRACT FROM AUTHOR]

A convenient and efficient strategy for the preparation of 2-sulfonylindoles has been achieved through iodophor-/H2O2-mediated 2-sulfonylation of indoles with readily available sulfonyl hydrazides in the aqueous phase. Iodophor is commercially available and serves as the green catalyst and aqueous phase. A series of 2-sulfonylated products from indoles and N-methylpyrrole were synthesized in moderate yields in only 10 min. Control experiments were also conducted to reveal the mechanism of action. This method is environment friendly, easy to operate and suitable for a wide range of substrates. [ABSTRACT FROM AUTHOR]

Flavin-containing monooxygenase from Methylophaga sp. (mFMO) was previously discovered to be a valuable biocatalyst used to convert small amines, such as trimethylamine, and various indoles. As FMOs are also known to act on sulfides, we explored mFMO and some mutants thereof for their ability to convert prochiral aromatic sulfides. We included a newly identified thermostable FMO obtained from the bacterium Nitrincola lacisaponensis (NiFMO). The FMOs were found to be active with most tested sulfides, forming chiral sulfoxides with moderate-to-high enantioselectivity. Each enzyme variant exhibited a different enantioselective behavior. This shows that small changes in the substrate binding pocket of mFMO influence selectivity, representing a tunable biocatalyst for enantioselective sulfoxidations. [ABSTRACT FROM AUTHOR]

Simple Summary: Pancreatic ductal adenocarcinoma has a low 5-year survival rate due to delayed diagnosis, rapid growth, tumor complexity, and difficulties in surgical resection. Treatments involving new targeted chemotherapeutic options are required due to challenges such as drug resistance, low efficacy, severe toxicity, high metastatic potential, and clinical trial failures. This study demonstrates the preclinical efficacy and potential of the novel combination of abemaciclib and panobinostat in multiple pancreatic cancer cell lines. Our results depict that a novel combination of these agents aids in synergistic effects, causing cell death in pancreatic cancer cells. The current 5-year survival rate of pancreatic cancer is about 12%, making it one of the deadliest malignancies. The rapid metastasis, acquired drug resistance, and poor patient prognosis necessitate better therapeutic strategies for pancreatic ductal adenocarcinoma (PDAC). Multiple studies show that combining chemotherapeutics for solid tumors has been successful. Targeting two distinct emerging hallmarks, such as non-mutational epigenetic changes by panobinostat (Pan) and delayed cell cycle progression by abemaciclib (Abe), inhibits pancreatic cancer growth. HDAC and CDK4/6 inhibitors are effective but are prone to drug resistance and failure as single agents. Therefore, we hypothesized that combining Abe and Pan could synergistically and lethally affect PDAC survival and proliferation. Multiple cell-based assays, enzymatic activity experiments, and flow cytometry experiments were performed to determine the effects of Abe, Pan, and their combination on PDAC cells and human dermal fibroblasts. Western blotting was used to determine the expression of cell cycle, epigenetic, and apoptosis markers. The Abe-Pan combination exhibited excellent efficacy and produced synergistic effects, altering the expression of cell cycle proteins and epigenetic markers. Pan, alone and in combination with Abe, caused apoptosis in pancreatic cancer cells. Abe-Pan co-treatment showed relative safety in normal human dermal fibroblasts. Our novel combination treatment of Abe and Pan shows synergistic effects on PDAC cells. The combination induces apoptosis, shows relative safety, and merits further investigation due to its therapeutic potential in the treatment of PDAC. [ABSTRACT FROM AUTHOR]

Simple Summary: Indocyanine green (ICG) is a dye that helps surgeons see the blood supply to tissues. In this study, (MIRRORS ICG) researchers wanted to see if this dye could help find cancer in women with advanced ovarian cancer undergoing robotic surgery after chemotherapy. After injecting ICG, a special camera was used to look at the whole abdomen and pelvic area. In this study, 102 tissue samples were taken to see if ICG helped identify cancerous tissue. The results showed that ICG correctly identified cancer in 91.1% of cases but had a low specificity of 13.0%, meaning it often falsely indicated cancer. This technique did not significantly help in detecting cancer in patients with widespread disease, but it showed some potential in those who had responded well to chemotherapy and had few remaining cancer spots. Molecular imaging with targeted dyes could enhance precision surgery in the future. Indocyanine green (ICG) is a fluorescent dye used for sentinel lymph node assessment and the assessment of perfusion in skin flaps and bowel anastomoses. ICG binds serum proteins and behaves as a macromolecule in the circulation. Tumour tissue has increased vascular permeability and reduced drainage, causing macromolecules to accumulate within it. MIRRORS ICG is designed to determine whether indocyanine green (ICG) helped identify metastatic deposits in women undergoing robotic interval cytoreductive surgery for advanced-stage (3c+) ovarian cancer. Peritoneal surfaces of the abdominal and pelvic cavity were inspected under white light and near-infrared light (da Vinci Si and Xi Firefly Fluorescence imaging, Intuitive Surgical Inc.) following intravenous injection of 20 mg ICG in sterile water. Visibly abnormal areas were excised and sent to histopathology, noting IGC positivity. In total, 102 biopsies were assessed using ICG. Intravenous ICG assessment following neoadjuvant chemotherapy had a sensitivity of 91.1% (95% CI [82.6–96.4%]), a specificity of 13.0% (95% CI [2.8–33.6%]), a positive predictive value of 78.3% (95% CI [68.4–86.2%]), and a negative predictive value of 30.0% (95% CI [6.7–65.2%]) False-positive samples were seen in 9/20 patients. Psammoma bodies were noted in the histopathology reports of seven of nine of these patients with false-positive results, indicating that a tumour had been present (chemotherapy-treated disease). This study demonstrates the appearance of metastatic peritoneal deposits during robotic cytoreductive surgery following the intravenous administration of ICG in women who have undergone neoadjuvant chemotherapy for stage 3c+ advanced ovarian cancer. A perfusion assessment using indocyanine green (ICG) peritoneal angiography during robotic interval cytoreductive surgery for advanced ovarian cancer did not clinically improve metastatic disease identification in patients with high-volume disease. The use of ICG in patients with excellent response to chemotherapy where few tumour deposits remained shows some promise. The potential of molecular imaging to enhance precision surgery and improve disease identification using the robotic platform is a novel avenue for future research. [ABSTRACT FROM AUTHOR]

Azide-containing compounds, organic azides, showcases a variety of reactivities, making them highly convenient and chameleonic intermediates. An indoline derivative has been proven to be of great significance in drug discovery due to its sp3-rich property. In this context, it is interesting to perform such vigorous azidation on medicinal-relevant indoles/indolines, resulting in the production of sp3-rich azidoindolines. The potential biological activity, in combination with the sp3-rich indoline bearing the azido moiety, makes azidoindolines an attractive synthetic target for medicinal and synthetic chemists. This review describes recent advances in the synthesis and application of azidoindolines: (1) iodine-mediated azidations, (2) metal-catalyzed azidations, (3) electrochemical azidations, (4) photochemical azidations, (5) azidation using a combination of an oxidant and an azide source, and (6) nucleophilic azidation. [ABSTRACT FROM AUTHOR]

To explore the long-term outcome of intracranial- intracranial side - to - side bypass for complex intracranial aneurysms. Methods Five patients with complex intracranial aneurysms underwent intracranial-intracranial side-to-side bypass performed by the same surgeon at The First Hospital of China Medical University from January 2015 to December 2023 were included. Two cases involved the A2 segment of anterior cerebral artery (ACA) and 3 cases involved the M2 segment of middle cerebral artery (MCA). Indocyanine green angiography (ICGA) was used intraoperatively, and CTA or DSA was used postoperatively to evaluate aneurysm occlusion and blood flow reconstruction. The modified Rankin Scale (mRS) was used to evaluate the neurological prognosis at one week, 3 months and the last follow-up. CT/MRI examination was completed on the first day, one week and 3 months after operation to evaluate whether hemorrhagic or ischemic complications occurred. Results Five cases of complex intracranial aneurysms were all occluded accurately. Two cases underwent A3-A3 side-to-side anastomosis, and 3 cases underwent M2-M2 side-to-side anastomosis, among which one case added M1-radial artery (RA)-M2 intracranial -intracranial bypass with RA as graft on the basis of M2-M2 side-to-side anastomosis. During the operation, ICGA confirmed that the side-to-side anastomosis and M1-RA-M2 bypass were unobstructed in 5 cases. The postoperative follow-up time was 23 (14, 71) months. No aneurysm was found in cerebrovascular imaging examination one week and 3 months after operation in 5 patients, and 9 to 12 months after operation in 3 patients. Five side - to - side anastomosis stomas and one M1-RA-M2 graft were all unobstructed. At one week after operation, the mRS increased by 0-3 score compared with that before operation (4 score maintained unchanged before and after operation in one case, 2 score increased in one case, and 3 score increased in one case). In 2 unruptured cases, the mRS score was 1 score at one week after operation, and there was no change from that before operation. At 3 months after operation, the mRS scores of 5 cases were decreased (2 cases with 0 score, one case with 2 score, and 2 cases with 3 score); one case was lost at the last follow-up, and the mRS scores of other 4 cases decreased further (2 cases with 0 score, one case with 1 score, and one case with 2 score). No cerebral hemorrhage or cerebral ischemia occurred in the follow-up. Conclusions Intracranial-intracranial side-to-side bypass has good short-term and long-term patency and stable long-term clinical effect. It is a reliable technique for surgical treatment of complex intracranial aneurysms [ABSTRACT FROM AUTHOR]

Introduction: Central Serous Chorioretinopathy (CSC), a leading cause of vision loss, presents diverse treatment challenges based on its acute or chronic manifestation. Areas covered: In acute CSC, treatment typically involves observation, reserving intervention for cases where optimal vision is crucial for professional activities. Emerging evidence advocates the use of half-dose or half-fluence Photodynamic Therapy (PDT), directed by Indocyanine Green Angiography (ICGA) or Fluorescein Angiography (FA), to hasten subretinal fluid (SRF) resolution, improve vision, and minimize recurrence. Chronic CSC, on the other hand, increasingly favors half-dose PDT, a recommendation strengthened by studies such as the PLACE trial. CSC complicated by Choroidal Neovascularization (CNV) necessitates management through intravitreal anti-Vascular Endothelial Growth Factor (anti-VEGF) injections and/or half-dose PDT. In cases of polypoidal choroidal vasculopathy (PCV), a combination of anti-VEGF therapy with PDT proves beneficial. For scenarios where standard treatments are impractical, Eplerenone emerges as the primary oral medication. Methods: A literature search of all original articles was performed using the major online databases. The following keywords 'Central Serous Chorioretinopathy' and 'Treatment,' were searched in combination with 'Photodynamic therapy,' 'Focal Laser Photocoagulation,' 'Subthreshold Micropulse Laser' and 'Systemic treatments.' Expert opinion: Managing CSC requires a patient-centered approach. In acute CSC, careful monitoring and lifestyle modifications may suffice, while in chronic CSC, PDT is a primary therapeutic option. [ABSTRACT FROM AUTHOR]

Summary: Radioresistance is an inevitable obstacle in the clinical treatment of inoperable patients with non-small cell lung cancer (NSCLC). Combining treatment with radiosensitizers may improve the efficacy of radiotherapy. Previously, the quinoline derivative 10E as new exporter of Nur77 has shown superior antitumor activity in hepatocellular carcinoma. Here, we aimed to investigate the radiosensitizing activity and acting mechanisms of 10E. In vitro, A549 and H460 cells were treated with control, ionizing radiation (IR), 10E, and 10E + IR. Cell viability, apoptosis, and cycle were examined using CCK-8 and flow cytometry assays. Protein expression and localization were examined using western blotting and immunofluorescence. Tumor xenograft models were established to evaluate the radiosensitizing effect of 10E in vivo. 10E significantly inhibited cell proliferation and increased their radiosensitivity while reducing level of p-BCRA1, p-DNA-PKs, and 53BP1 involved in the DNA damage repair pathway, indicating that its radiosensitizing activity is closely associated with repressing DNA damage repair. A549 cells showed low level of Nur77 and a low response to IR but 10E-treated A549 cells showed high level of Nur77 indicating that Nur77 is a core radiosensitivity factor and 10E restores the expression of Nur77. Nur77 and Ku80 extranuclear co-localization in the 10E-treated A549 cells suggested that 10E-modulated Nur77 nuclear exportation inhibits DNA damage repair pathways and increases IR-triggered apoptosis. The combination of 10E and IR significantly inhibits tumor growth in a tumor xenograft model. Our findings suggest that 10E acts as a radiosensitizer and that combining 10E with radiotherapy may be a potential strategy for NSCLC treatment. [ABSTRACT FROM AUTHOR]

Periodontitis, the second most common oral disease, is primarily initiated by inflammatory responses and osteoclast differentiation, in which the MAPK signaling pathway and mitochondrial function play important roles. 3‐methyl‐1H‐indol‐1‐yl dimethylcarbamodithioate (3o), a hybrid of indole and dithiocarbamate, was first synthesized by our group. It has shown anti‐inflammatory activity against lipopolysaccharide‐induced acute lung injury. However, it is not known if 3o can exert effects in periodontitis. In vitro study: LPS‐induced macrophage inflammation initiation and a receptor activator of nuclear factor κB ligand‐stimulated osteoclast differentiation model were established. Cell viability, inflammatory cytokines, osteoclast differentiation, the MAPK signaling pathway, and mitochondrial function before and after treatment with 3o were investigated. In vivo study: Alveolar bone resorption, inflammatory cytokine expression, osteoclast differentiation, and the underlying mechanisms were assessed in mice with periodontitis. Inflammatory cytokine expression and osteoclast differentiation appeared downregulated after 3o treatment. 3o inhibited the MAPK signaling pathway and restored mitochondrial function, including mitochondrial reactive oxygen species, mitochondrial membrane potential, and ATP production. Meanwhile, 3o reduced inflammation activation and bone resorption in mice with periodontitis, reflected by the decreased expression of inflammatory cytokines and osteoclasts, implying that 3o inhibited the MAPK signaling pathway and the mitochondrial oxidative DNA damage marker 8‐OHdG. These results highlight the protective role of 3o in periodontitis in mice and reveal an important strategy for preventing periodontitis. [ABSTRACT FROM AUTHOR]

Plant growth regulators (PGRs) are involved in multiple aspects of plant life, including plant growth, development, and response to environmental stimuli. They are also vital for the formation of secondary metabolites in various plants. Salvia miltiorrhiza is a famous herbal medicine and has been used commonly for > 2000 years in China, as well as widely used in many other countries. S. miltiorrhiza is extensively used to treat cardiovascular and cerebrovascular diseases in clinical practices and has specific merit against various diseases. Owing to its outstanding medicinal and commercial potential, S. miltiorrhiza has been extensively investigated as an ideal model system for medicinal plant biology. Tanshinones and phenolic acids are primary pharmacological constituents of S. miltiorrhiza. As the growing market for S. miltiorrhiza, the enhancement of its bioactive compounds has become a research hotspot. S. miltiorrhiza exhibits a significant response to various PGRs in the production of phenolic acids and tanshinones. Here, we briefly review the biosynthesis and signal transduction of PGRs in plants. The effects and mechanisms of PGRs on bioactive compound production in S. miltiorrhiza are systematically summarized and future research is discussed. This article provides a scientific basis for further research, cultivation, and metabolic engineering in S. miltiorrhiza. [ABSTRACT FROM AUTHOR]

A new method for the synthesis of 2-(phenyl)indole via the cyclization of 2-(phenylethynyl)aniline in the presence of K2S was established, which was used to prepare 2-(phenyl)indole derivatives in high yields (66%-93%). Mechanistic studies have revealed that a trisulfur radical anion (S3•−) is generated from K2S, which acts as an initiator for the intramolecular addition of the alkyne and the amino group in o-alkynylaniline, ultimately leading to the formation of the indole derivative. This method provides a new way to prepare 2-(phenyl)indoles and a novel application of S3•− in organic synthesis. [ABSTRACT FROM AUTHOR]

The chemical valorization of widespread molecules in renewable sources is a field of research widely investigated in the last decades. In this context, we envisaged that indole-3-carbinol, present in different Cruciferae plants, could be a readily available building block for the synthesis of various classes of indoles through a palladium-catalyzed Tsuji–Trost-type reaction with O and S soft nucleophiles. The regiochemical outcome of this high-yielding functionalization shows that the nucleophilic substitution occurs only at the benzylic position. Interestingly, with this protocol, the sulfonyl unit could be appended to the indole nucleus, providing convenient access to new classes of molecules with potential bioactivity. [ABSTRACT FROM AUTHOR]

Simple Summary: A positive sentinel lymph node biopsy of cutaneous melanoma patients has a substantial impact on subsequent treatment decisions. The standard of care approach to identify the sentinel lymph node is technetium (Tc)-based lymphoscintigraphy. This technique comes with a radiation exposure and high costs. Indocyanine green (ICG)-based near-infrared fluorescence imaging could be an alternative if demonstrated to have a comparable diagnostic accuracy. Therefore, a systematic literature review and meta-analysis were conducted considering studies comparing the accuracy of ICG and Tc for intraoperative guidance. Within the seven included studies, no significant differences between the two modalities were found regarding the identification of metastatic patients or the false negative rate. ICG may be a non-inferior alternative to Tc for intraoperative identification of the sentinel lymph node in cutaneous melanoma patients. The standard of care approach to identify sentinel lymph nodes (SLNs) in clinically non-metastatic cutaneous melanoma patients is technetium (Tc)-based lymphoscintigraphy. This technique is associated with radiation exposure, a long intervention time, high costs, and limited availability. Indocyanine green (ICG)-based near-infrared fluorescence imaging offers a potential alternative if proven to be of comparable diagnostic accuracy. While several clinical cohorts have compared these modalities, no systematic review exists that provides a quantitative analysis of their results. Hence, a systematic literature review was conducted in December 2023 considering clinical studies comparing the diagnostic accuracy of ICG and Tc for sentinel lymph node biopsy in cutaneous melanoma patients. Three hundred nineteen studies were identified and further screened in accordance with the PRISMA 2020 guidelines, resulting in seven studies being included in the final meta-analysis. Tc identified a significantly higher number of SLNs and metastatic SLNs in prospective studies only. However, in the overall meta-analysis of all included comparative studies, no significant differences were found regarding the identification of metastatic patients or the false negative rate (FNR). ICG may be a non-inferior alternative to Tc for intraoperative guidance in sentinel lymph node biopsy in cutaneous melanoma patients. Future randomized controlled trials are needed, especially regarding the preoperative, transcutaneous identification of the affected lymph node basin. [ABSTRACT FROM AUTHOR]

Indoline‐fused polycycles are commonly found as a key structural component in numerous natural products and biologically active compounds. In recent times, the incorporation of sulfonyl fluoride groups has drawn significant attention in research due to their potential to enhance or confer new biological activities to molecules. In this study, we report the development of a modular approach for synthesizing FSO2‐functionalized cyclobutane‐fused indolines by employing an intermolecular [2+2] cycloaddition reaction between indoles and SuFExable ethenesulfonyl fluoride under triplet energy‐transfer catalysis. This method features mild reaction conditions, metal‐free photocatalysts, and excellent tolerance to various functional groups. Moreover, we demonstrate the feasibility of further modifying the FSO2‐functionalized indoline products via SuFEx click reactions, enabling their conjugation with other molecules. [ABSTRACT FROM AUTHOR]

This document provides information on the use of photoacid generators (PAGs) in catalysis, specifically in the Friedel-Crafts alkylation of indoles with aldehydes/ketones. The study focuses on diarylethenes and terarylenes as PAGs, which have advantages such as high quantum yields and autonomy. The researchers developed an environmentally friendly method for synthesizing diindolylmethane derivatives with potential antibacterial, antitumor, and antifungal activities. The document also provides detailed information on the synthesis and characterization of various compounds, including their physical properties and spectroscopic data. This information can be useful for researchers studying these compounds and their properties. [Extracted from the article]

Aqueous soluble and stable Cu(I) molecular catalysts featuring a catenane ligand composed of two dicationic, mutually repelling but mechanically interlocked macrocycles are reported. The ligand interlocking not only fine‐tunes the coordination sphere and kinetically stabilizes the Cu(I) against air oxidation and disproportionation, but also buries the hydrophobic portions of the ligands and prevents their dissociation which are necessary for their good water solubility and a sustained activity. These catenane Cu(I) complexes can catalyze the oxidative C−C coupling of indoles and tetrahydroisoquinolines in water, using H2O2 as a green oxidant with a good substrate scope. The successful use of catenane ligands in exploiting aqueous Cu(I) catalysis thus highlights the many unexplored potential of mechanical bond as a design element for exploring transition metal catalysis under challenging conditions. [ABSTRACT FROM AUTHOR]

The development of sustainable protocols for the synthesis of alkylated heteroarenes is crucial owing to their widespread existence in medicinally relevant and bioactive natural products. Herein, we describe an efficient, additive‐ and solvent‐free approach for the regioselective C−H alkylation of indoles and azoles with alkenes using a nickel catalyst, which proceeds through a chelation‐assistance strategy. The reaction exclusively provided branched alkylated products with the compatibility of alkyl, alkoxy, fluoro, trifluoromethyl, alkene, cyano, ester, and carbonyl groups. This protocol is applicable to other heteroarenes, such as imidazoles and benzimidazoles, providing the desired alkylated products with exclusive Markovnikov selectivity. The synthetic utility and scale‐up of the reaction are demonstrated, and the protocol is in concord with the principles of green chemistry. Alkylation proceeds through facile and reversible C−H nickelation and alkene insertion processes, presumably involving rate‐limiting reductive elimination. [ABSTRACT FROM AUTHOR]