Hydrosilylation of Arynes with Silanes and Silicon-Based Polymer.

Benzyne derived from hexadehydrogenated Diels Alder (HDDA) reactions was found to be an efficient hydrosilylation acceptors. Various silanes can react smoothly with HDDA-derived benzyne to give the arylation products. Lewis acid such as boron trifluoride etherate can accelerate these hydrosilylation reactions. Polyhydromethylsiloxane (PHMS), a widely used organosilicon polymer, was also successfully modified using our method. About 5 % of Si-H bonds in the polymer were inserted by benzynes, giving a functional PHMS with much more solubility in methanol and with a blue-emitting fluorescence behavior. Mechanism research shows that the insertion of benzyne into the Si-H bond probably undergoes a synergistic pathway, which is quite different from the traditional radical-initiated hydrosilylation or transition-metal-catalyzed hydrosilylation.

The Cytochalasins and Polyketides from a Mangrove Endophytic Fungus Xylaria arbuscula QYF.

Twelve compounds, including four undescribed cytochalasins, xylariachalasins A-D (1-4), four undescribed polyketides (5-8), and four known cytochalasins (9-12), were isolated from the mangrove endophytic fungus Xylaria arbuscula QYF. Their structures and absolute configurations were established by extensive spectroscopic analyses (1D and 2D NMR, HRESIMS), electronic circular dichroism (ECD) calculations, 13C NMR calculation and DP4+ analysis, single-crystal X-ray diffraction, and the modified Mosher ester method. Compounds 1 and 2 are rare cytochalasin hydroperoxides. In bioactivity assays, Compound 2 exhibited moderate antimicrobial activities against Staphylococcus aureus and Candida albicans with MIC values of 12.5 µM for both Compound 10 exhibited significant cytotoxic activity against MDA-MB-435 with an IC50 value of 3.61 ± 1.60 µM.

Carbene-catalyzed [3 + 2 + 1] annulation via C-N radical coupling of iminyl radicals and ketyl radicals.

An N-heterocyclic carbene-catalyzed cascade [3 + 2 + 1] annulation to assemble vinyl azides, aldehydes, and trihalomethyl reagents (Togni's reagent or CCl4) towards 1,3-oxazin-6-ones was reported. The cascade was triggered by an NHC-catalyzed single electron transfer (SET) between aldehydes and trihalomethyl reagents, followed by the addition of trihalomethyl radicals to vinyl azides, a denitrogenated transformation into iminyl radicals, a C-N radical coupling of iminyl radicals and ketyl radicals, and a base-controlled dehalogenative cyclization.

Direct Arylation of Silicon Nanocrystals with Hexadehydro-Diels-Alder-Derived Benzynes.

Colloidal silicon nanocrystals (SiNCs) have garnered significant interest in optoelectronics and biomedical applications. Direct arylation provides pathways to enhance the solution processability of particles and manipulate the photophysical and electronic properties of SiNCs. Unfortunately, existing methods employed to prepare aryl-functionalized SiNCs are based on organometallic coupling or transition-metal-catalyzed strategies, which require metal-based reagents for preactivation or the precursors and complicated post-treatment processes for product purification. Herein, we demonstrate a metal-free method that directly functionalizes SiNCs with aryl-based ligands. We design a series of benzyne derivatives formed from the thermal cyclization of predesigned alkynes, allowing efficient arylation on hydride-terminated silicon surfaces under mild conditions. These aryl-functionalized SiNCs exhibit strong blue emissions with nanosecond-scaled decay, suggesting the formation of a new radiative recombination channel on SiNC surfaces.

The eco-friendly electrosynthesis of trifluoromethylated spirocyclic indolines and their anticancer activity.

A method for the electrochemical diastereoselective oxytrifluoromethylation of indoles was developed for the eco-friendly synthesis of CF3-containing spirocyclic indolines. The cascade reaction comprised anodic oxidation to obtain CF3 radicals, the addition of radicals to indoles, and intramolecular spirocyclization. The reaction system without external chemical oxidants could easily be scaled up. Antiproliferation assays of these CF3-substituted spirocyclic indolines exhibited their promising activities and selectivities toward several types of cancer cells, including Huh-7, A549, and cisplatin-resistant cancer cells (A549/DDP).

Atroposelective Arene Formation by Carbene-Catalyzed Formal [4+2] Cycloaddition.

Atroposelective arene formation is an efficient method to build axially chiral molecules with multi-substituted arenes. Reported here is an organocatalyzed atroposelective arene formation reaction by an N-heterocyclic carbene (NHC) catalyzed formal [4+2] cycloaddition of conjugated dienals and α-aryl ketones. This study expands the synthetic potential of NHC organocatalysis and provides a competitive pathway for the synthesis of axially chiral ligands, catalysts, and other functional molecules.

Access to All-Carbon Spirocycles through a Carbene and Thiourea Cocatalytic Desymmetrization Cascade Reaction.

A new catalytic approach for rapid asymmetric access to spirocycles is disclosed. The reaction involves a carbene- and thiourea-cocatalyzed desymmetrization process with the simultaneous installation of a spirocyclic core. The use of a thiourea cocatalyst is critical to turn on this reaction, as no product was formed in the absence of a thiourea. Our study constitutes the first success in the carbene-catalyzed enantioselective synthesis of all-carbon spirocycles. The reaction products can be readily transformed into sophisticated multicyclic molecules and chiral ligands.

Carbene-Catalyzed Desymmetrization and Direct Construction of Arenes with All-Carbon Quaternary Chiral Center.

Multisubstituted arenes such as indanes with attached all-carbon quaternary centers are unique scaffolds in synthetic functional molecules and sophisticated natural products. A key challenge in preparing such molecules lies in the enantioselective installation of the quaternary carbon centers. Conventional methods in this direction include asymmetric substitution reactions and substrate-controlled cyclization reactions. These reactions lead to poor stereoselectivities and/or require long and tedious synthetic steps. Disclosed here is a one-step organic catalytic strategy for enantioselective access to this class of molecules. The reaction involves an N-heterocyclic carbene catalyzed process for direct benzene construction, indane formation, remote-carbon desymmetrization, and excellent chirality control. This approach will enable the concise synthesis of arene-containing molecules, including those with complex structures and challenging chiral centers.

N-Heterocyclic Carbene-Catalyzed δ-Carbon LUMO Activation of Unsaturated Aldehydes.

An N-heterocyclic carbene (NHC) catalyzed domino reaction triggered by a δ-LUMO activation of α,ß-γ,δ-diunsaturated enal has been developed for the formal [4 + 2] construction of multisubstituted arenes and 3-ylidenephthalide. These two products, formed in a highly chemo- and regioselective manner, were obtained via different catalytic pathways due to a simple change of the substrate. The activation of the remote δ-carbon of unsaturated aldehydes expands the synthetic potentials of NHC organocatalysis.

Access to oxoquinoline heterocycles by N-heterocyclic carbene catalyzed ester activation for selective reaction with an enone.

Organocatalytic ester activation is developed for a highly selective cascade reaction between saturated esters and amino enones. The reaction involves activation of the ß-carbon atom of the ester as a key step. This method allows a single-step access to multicyclic oxoquinoline-type heterocycles with high enantiomeric ratios.

Rhodium-catalyzed enantioselective addition to unsymmetrical α-diketones: tandem one-pot synthesis of optically active 3-tetrasubstituted isochroman derivatives.

The domino effect: An efficient and general catalytic one-pot synthesis of quaternary-substituted isochroman derivatives has been developed (see scheme). The cascade transformation relies on rhodium-catalyzed highly regio- and enantioselective 1,2-addition of arylboronic acids to unsymmetrical α-diketones and intramolecular etherification or esterification, and provides a variety of enantioenriched isochromanones under exceptionally mild conditions.

Rhodium-catalyzed enantioselective 1,2-addition of arylboronic acids to heteroaryl α-ketoesters for synthesis of heteroaromatic α-hydroxy esters.

The first example of catalytic asymmetric 1,2-addition of arylboronic acids to heteroaryl α-ketoesters has been developed for the highly efficient and enantioselective synthesis of quaternary carbon-containing heteroaromatic α-hydroxy esters. The reaction works well with a variety of α-ketoesters including 3-indoleglyoxylates, 3-benzofuranglyoxylates and 3-benzothiopheneglyoxylates under very mild conditions, affording the corresponding products in moderate to good yields with high enantiomeric excesses (up to 97%).

Design of N-cinnamyl sulfinamides as new sulfur-containing olefin ligands for asymmetric catalysis: achieving structural simplicity with a categorical linear framework.

The design and development of an extraordinarily interesting new class of chiral sulfur-olefin hybrid ligands with remarkable structural simplicity were described. These unique sulfinamide-olefin ligands have been proved to be highly effective ligands in rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids to α,ß-unsaturated carbonyl compounds (up to 99% yield and 98% ee).

Electroredox carbene organocatalysis with iodide as promoter.

Oxidative carbene organocatalysis, inspired from Vitamin B1 catalyzed oxidative activation from pyruvate to acetyl coenzyme A, have been developed as a versatile synthetic method. To date, the α-, ß-, γ-, δ- and carbonyl carbons of (unsaturated)aldehydes have been successfully activated via oxidative N-heterocyclic carbene (NHC) organocatalysis. In comparison with chemical redox or photoredox methods, electroredox methods, although widely used in mechanistic study, were much less developed in NHC catalyzed organic synthesis. Herein, an iodide promoted electroredox NHC organocatalysis system was developed. This system provided general solutions for electrochemical single-electron-transfer (SET) oxidation of Breslow intermediate towards versatile transformations. Radical clock experiment and cyclic voltammetry results suggested an anodic radical coupling pathway.

Progress in the Electrochemical Reactions of Sulfonyl Compounds.

Electrosynthesis has recently attracted more and more attention due to its great potential to replace chemical oxidants or reductants in molecule-electrode electron transfer. Sulfonyl compounds such as sulfonyl hydrazides, sulfinic acids (and their salts), sulfonyl halides have been discovered as practical precursors of several radicals. As electrochemical redox reactions can provide green and efficient pathways for the activation of sulfonyl compounds, studies for electrosynthesis have rapidly increased. Several types of radicals can be generated from anodic oxidation or cathodic reduction of sulfonyl compounds and can initiate fluoroalkylation, benzenesulfonylation, cyclization or rearrangement. In this Review, we summarize the electrosynthesis developments involving sulfonyl compounds mainly in the last decade.

Case report: Two PD-L1 positive unresectable advanced pancreatic carcinoma patients with microsatellite stability achieved R0 resection after PD-1 antibody plus chemotherapy as a successful downstaging therapy: A report of two cases.

Background: Nonobvious early symptoms are a prominent characteristic of pancreatic cancer, resulting in only 20% of patients having resectable tumors at the time of diagnosis. The optimal management of unresectable advanced pancreatic cancer (UAPC) remains an open research question. In this study, the tumors shrank significantly after PD-1 antibody combined with chemotherapy in two UAPC patients, and both have achieved R0 (pathologically negative margin) resection and survival to date. Case presentation: Case 1: A 53-year-old man was diagnosed with pancreatic adenocarcinoma (Stage III). He received six cycles of PD-1 antibody plus chemotherapy as the first-line treatment. The tumor was reduced from 11.8×8.8 cm to "0" (the pancreatic head was normal as shown by enhanced computed tomography, ECT) after preoperative neoadjuvant therapy (PNT) and the adverse effects were tolerable. The patient underwent radical surgery and achieved R0 resection. Case 2: A 43-year-old man diagnosed with pancreatic adenocarcinoma with liver metastasis (Stage IV) received three cycles of PD-1 antibody combined with chemotherapy. The tumor was reduced from 5.2×3.9 cm to 2.4×2.3 cm with no side effects. The patient also underwent radical surgery and achieved R0 resection. Conclusion: PD-1 antibody plus a chemotherapy regimen resulted in a surprising curative effect and safety in two patients with UAPC, which may portend an improvement in pancreatic carcinoma treatment. We may have a way for UAPC patients to obtain radical treatment and gain long-term survival. Two PD-L1 positive UAPC patients with microsatellite stability (MSS) enlighten us to have a more comprehensive understanding of the prediction of immunotherapy.

Electrochemical synthesis of colloidal lead- and bismuth-based perovskite nanocrystals.

Metal halide perovskite nanocrystals (PNCs) have aroused worldwide research interest for optoelectronics. Herein, we report the first electrochemical approach to prepare colloidal PNCs with drastically reduced consumption of salts, solvents, and ligands. This method can be extended to prepare mixed-halide and bismuth-based PNCs by changing precursor compositions and metal components.

Assembly of multicyclic isoquinoline scaffolds from pyridines: formal total synthesis of fredericamycin A.

The construction of an isoquinoline skeleton typically starts with benzene derivatives as substrates with the assistance of acids or transition metals. Disclosed here is a concise approach to prepare isoquinoline analogues by starting with pyridines to react with ß-ethoxy α,ß-unsaturated carbonyl compounds under basic conditions. Multiple substitution patterns and a relatively large number of functional groups (including those sensitive to acidic conditions) can be tolerated in our method. In particular, our protocol allows for efficient access to tricyclic isoquinolines found in hundreds of natural products with interesting bioactivities. The efficiency and operational simplicity of introducing structural complexity into the isoquinoline frameworks can likely enable the collective synthesis of a large set of natural products. Here we show that fredericamycin A could be obtained via a short route by using our isoquinoline synthesis as a key step.

Stabilized Molybdenum Trioxide Nanowires as Novel Ultrahigh-Capacity Cathode for Rechargeable Zinc Ion Battery.

Exploration of high-performance cathode materials for rechargeable aqueous Zn ion batteries (ZIBs) is highly desirable. The potential of molybdenum trioxide (MoO3) in other electrochemical energy storage devices has been revealed but held understudied in ZIBs. Herein, a demonstration of orthorhombic MoO3 as an ultrahigh-capacity cathode material in ZIBs is presented. The energy storage mechanism of the MoO3 nanowires based on Zn2+ intercalation/deintercalation and its electrochemical instability mechanism are particularly investigated and elucidated. The severe capacity decay of the MoO3 nanowires during charging/discharging cycles arises from the dissolution and the structural collapse of MoO3 in aqueous electrolyte. To this end, an effective strategy to stabilize MoO3 nanowires by using a quasi-solid-state poly(vinyl alcohol)(PVA)/ZnCl2 gel electrolyte to replace the aqueous electrolyte is developed. The capacity retention of the assembled ZIBs after 400 charge/discharge cycles at 6.0 A g-1 is significantly boosted, from 27.1% (in aqueous electrolyte) to 70.4% (in gel electrolyte). More remarkably, the stabilized quasi-solid-state ZIBs achieve an attracting areal capacity of 2.65 mAh cm-2 and a gravimetric capacity of 241.3 mAh g-1 at 0.4 A g-1, outperforming most of recently reported ZIBs.

Engineering channels of metal-organic frameworks to enhance catalytic selectivity.

This report describes a facile strategy to enhance the catalytic selectivity by tuning the pore sizes of metal-organic frameworks (MOFs) in nanoparticles (NPs)/MOF composite catalysts. A general post-synthetic modification method was used to adjust the pore sizes of MOFs by using anhydrides with different chain lengths to react with amino groups in the ligands. The modified NPs/MOF catalysts exhibited enhanced size selectivity performance in the hydrogenation of olefins, which revealed the flexibility of MOFs as supporting materials for heterogeneous catalysis.