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The control of noncarbon stereogenic centers is of profound importance owing to their enormous interest in bioactive compounds and chiral catalyst or ligand design for enantioselective synthesis. Despite various elegant approaches have been achieved for construction of S‐, P‐, Si‐ and B‐stereocenters over the past decades, the catalyst‐controlled strategies to govern the formation of N‐stereogenic compounds have garnered less attention. Here, we disclose the first organocatalytic approach for efficient access to a wide range of nitrogen‐stereogenic compounds through a desymmetrization approach. Intriguingly, the pro‐chiral remote diols, which are previously not well addressed with enantiocontrol, are well differentiated by potent chiral carbene‐bound acyl azolium intermediates. Preliminary studies shed insights on the critical importance of the ionic hydrogen bond (IHB) formed between the dimer aggregate of diols to afford the chiral N‐oxide products that feature a tetrahedral nitrogen as the sole stereogenic element with good yields and excellent enantioselectivities. Notably, the chiral N‐oxide products could offer an attractive strategy for chiral ligand design and discovery of potential antibacterial agrochemicals. [ABSTRACT FROM AUTHOR]

Prussian blue analogues (PBAs) are recognized as promising cathode materials for sodium‐ion batteries (SIBs) due to their facile synthesis, low‐cost, high capacity, and environmental friendliness. However, high water content (>10 wt%) in the framework and unsatisfactory structural stability of PBAs are still the bottlenecks for industrial applications. Herein, interstitial K‐doping is employed to minimize the interstitial water and enhance the structural stability of Na2‐xFeMn[Fe(CN)6] (FeMnPBA), thereby boosting the sodium storage performance. The 3% K‐doping (K‐FeMnPBA3) demonstrates a much‐reduced water content of 6.9%, accompanied by a notably enhanced capacity of 139.1 mAh g−1 at 100 mA g−1 and a remarkable capacity retention of 77.1% after 700 cycles. Furthermore, the K‐FeMnPBA3/hard carbon (HC) pouch cell achieves a stable cyclability with 82.6% capacity retention after 600 cycles. This research offers valuable insights into low‐water PBAs for practical applications in SIBs. [ABSTRACT FROM AUTHOR]

A series of novel thiazine derivatives featuring axial chirality in both (R) and (S) configurations were successfully synthesized by N‐heterocyclic carbene (NHC)‐catalyzed enantioselective [3 + 3] annulations, and their potential as anti‐plant virus agents against potato virus Y (PVY) was evaluated. Biological activity results demonstrated that most of these chiral thiazine derivatives exhibited significant activities against PVY. Notably, compound (S)‐3g displayed a remarkable 58% inactivation effect against PVY at a concentration of 500 μg/mL, slightly surpassing the effectiveness of Ningnanmycin (NNM) at 57%. Additionally, (S)‐3g exhibited curative activity of 57%, which is superior to NNM (53%). Molecular docking studies revealed preliminary insights into the distinct biological properties of the two different enantiomers, (R) or (S)‐3g against PVY, wherein single enantiomer (S)‐3g formed a more stable interaction with PVY‐CP, as indicated by its lower binding free energy (−41.18 kcal/mol) compared to (R)‐3g (−36.9 kcal/mol). The findings in this study with a new class of axially chiral thiazine derivatives shall inspire further development of chiral heterocycles as potential drug candidates for the protection of plant virus infections. [ABSTRACT FROM AUTHOR]

The direct functionalization of inert C(sp3)‐H bonds to form carbon‐carbon and carbon‐heteroatom bonds offers vast potential for chemical synthesis and therefore receives increasing attention. At present, most successes come from strategies using metal catalysts/reagents or photo/electrochemical processes. The use of organocatalysis for this purpose remains scarce, especially when dealing with challenging C−H bonds such as those from simple alkanes. Here we disclose the first organocatalytic direct functionalization/acylation of inert C(sp3)‐H bonds of completely unfunctionalized alkanes. Our approach involves N‐heterocyclic carbene catalyst‐mediated carbonyl radical intermediate generation and coupling with simple alkanes (through the corresponding alkyl radical intermediates generated via a hydrogen atom transfer process). Unreactive C−H bonds are widely present in fossil fuel feedstocks, commercially important organic polymers, and complex molecules such as natural products. Our present study shall inspire a new avenue for quick functionalization of these molecules under the light‐ and metal‐free catalytic conditions. [ABSTRACT FROM AUTHOR]

The development of catalytic synthetic approaches towards molecular complexity from simple materials continues to be an ultimate goal in synthetic chemistry. Over the past decades, N‐heterocyclic carbene (NHC) organocatalysis has been extensively investigated to provide opportunities for a vast number of novel chemical transformations. Various activation modes and reactive intermediates enabled by NHC small‐molecule catalysts, such as Breslow intermediates, (homo)enolates, acyl azoliums and their derived unsaturated azoliums exhibit great potential in the construction of complicated skeletons. This personal account will summarize our group's recent work in the exploration of new activation modes of NHC catalysis towards molecular complexity with a focus on the development and applications of NHC to achieve diversity and enantioselectivity in the preparation of functional molecules. [ABSTRACT FROM AUTHOR]

The development of catalyst‐controlled methods for direct functionalization of two distinct C−H bonds represents an appealing approach for C−C formations in synthetic chemistry. Herein, we describe an organocatalytic approach for straightforward acylation of C(sp3)−H bonds employing readily available aldehyde as "acyl source" involving dehydrogenative coupling of aldehydes with ether, amine, or benzylic C(sp3)−H bonds. The developed method affords a broad range of ketones under mild conditions. Mechanistically, simple ortho‐cyanoiodobenzene is essential in the oxidative radical N‐heterocyclic carbene catalysis to give a ketyl radical and C(sp3) radical through a rarely explored intermolecular hydrogen atom transfer pathway, rendering the acylative C−C formations in high efficiency under a metal‐ and light‐free catalytic conditions. Moreover, the prepared products show promising anti‐bacterial activities that shall encourage further investigations on novel agrochemical development. [ABSTRACT FROM AUTHOR]

The determination of the absolute configuration of chiral molecular entities by means of X‐ray crystallography is overall of central importance in stereochemistry. However, the growth of enantiopure single crystals often represents an unsurmountable and frustrating hurdle. Quasi‐racemic crystals of biomacromolecules, for which the absolute configuration is predetermined by the chiral monomers, allowed the X‐ray crystallographic analysis of systems that are difficult to crystallize as pure enantiomers, with aims other than the determination of the absolute structure. Taking advantage of the greater propensity of quasi‐racemic mixtures to co‐crystallize compared to growing enantiomerically pure crystals of a single compound, we herein describe the use of X‐ray crystallography of quasi‐racemates for the absolute configuration determination. We expect that this approach is particularly useful to establish the sense of selectivity in the development of stereoselective methods by simplified crystallizations, while confirming the consistent selectivity with a second molecular structure within the same measurement. [ABSTRACT FROM AUTHOR]

Quinone methides are fundamental intermediates for a wide range of reactions in which catalyst stereocontrol is often achieved by hydrogen bonding. Herein, we describe the feasibility of an intramolecular Friedel–Crafts 6π electrocyclization through ortho‐quinone methide iminiums stereocontrolled by a contact ion pair. A disulfonimide catalyst activates racemic trichloroacetimidate substrates and imparts stereocontrol in the cyclization step, providing a new avenue for selective ortho‐quinone methide iminium functionalization. A highly stereospecific oxidation readily transforms the enantioenriched acridanes into rotationally restricted acridiniums. Upon ion exchange, the method selectively affords atropisomeric acridinium tetrafluoroborate salts in high yields and an enantioenrichment of up to 93 : 7 e.r. We envision that ion‐pairing catalysis over ortho‐quinone methide iminiums enables the selective synthesis of a diversity of heterocycles and aniline derivatives with distinct stereogenic units. [ABSTRACT FROM AUTHOR]

The combined use of gold as transition metal catalyst and N‐heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo‐ and enantio‐selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co‐existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed. [ABSTRACT FROM AUTHOR]

A carbene and sulfinate co‐catalyzed intermolecular Rauhut–Currier reaction between enals and nitrovinyl indoles is disclosed. The carbene catalyst activates the enal and the sulfinate co‐catalyst activates the nitrovinyl indole. Both activation processes are realized via the formation of covalent bonds between the catalysts and substrates to generate catalyst‐bound intermediates. The dual catalytic reaction affords azepino[1,2‐a]indole products with excellent stereoselectivity. Our study demonstrates the unique involvement of sulfinate as an effective nucleophilic catalyst in activating electron‐deficient alkenes for asymmetric reactions. This dual catalytic approach should also encourage future explorations of both sulfinate and carbene catalysts for new reactions. It takes two: A carbene and sulfinate co‐catalyzed intermolecular Rauhut–Currier reaction provides an efficient method to access azepino[1,2‐a]indoles with excellent stereoselectivity. The sulfinate was found to be a unique and effective nucleophilic catalyst in activating nitrovinyl indoles for the Rauhut–Currier reaction. [ABSTRACT FROM AUTHOR]

Abstract: The common carp, Cyprinus carpio, is the third most cultivated freshwater species worldwide, but is also considered an invasive species. The Trojan Y chromosome strategy is one of the most promising methods to eradicate this invasive species. However, obtaining fertile YY supermale (MYY) and YY physiological female (FYY) common carp was thought to be very difficult. The present study focused on the production of androgenetic MYY and XY physiological female (FXY) common carp. We first optimized the conditions for artificially induced androgenesis. The results indicated that the optimum ultraviolet (UV) exposure time was 4 min at an irradiation distance of 26 cm and the optimum initiation time with heat shock (40 ± 0.5 C for 2 min) was 30 min after fertilization. Then, we produced androgenetic MYY Yellow River carp with only paternal inheritance, which were viable and identified by paternity testing and test crossing. Finally, we successfully produced FXY Yellow River carp by feeding 60‐d‐old MXY with commercially available feed mixed with 17β‐estradiol (200 mg/kg) and Flutamide (200 mg/kg) for 3 mo. In conclusion, by combining artificially induced androgenesis with an artificially induced sex reversal technique, we could cost‐effectively produce MYY and FXY common carp. [ABSTRACT FROM AUTHOR]

A carbene-catalyzed intermolecular C−N bond formation, which initiates a highly selective cascade reaction for the synthesis of pyrrolidine fused β-lactones, is disclosed. The nitrogen-containing bicyclic β-lactone products are obtained with good yields and excellent stereoselectivities. Synthetic transformations of the reaction products into useful functional molecules, such as amino catalysts, can be efficiently realized under mild reaction conditions. Mechanistically, this study provides insights into modulating the reactivities of heteroatoms, such as nitrogen atoms, in challenging carbene-catalyzed asymmetric carbon-heteroatom bond-forming reactions. [ABSTRACT FROM AUTHOR]

Simple and inexpensive polyhalides (CCl4 and C2Cl6) have been found to be effective and versatile oxidants in removing electrons from Breslow intermediates under N-heterocyclic carbene (NHC) catalysis. This oxidative reaction involves multiple single-electron-transfer (SET) processes and several radical intermediates. The α, β, and γ-carbon atoms of aldehydes and enals could be readily functionalized. Given the low cost of the oxidants and the broad applicability of the reactions, this study is expected to greatly enhance the feasibility of oxidative NHC catalysis for large-scale applications. Also this new SET radical process with polyhalides as single-electron oxidants will open a new avenue in the development of NHC-catalyzed radical reactions. [ABSTRACT FROM AUTHOR]

Ultralow Pt-loading Au nanoparticles have been fabricated on the surface of reduced graphene oxide (RGO) by using underpotential deposition (UPD) monolayer redox replacement process. The Pt/Au/RGO modified electrode exhibits an excellent electrocatalytic activity toward catechol and hydroquinone. Under the optimized condition, the separation of peak-to-peak between hydroquinone and catechol is 197 mV, which is wide enough to distinguish the isomers of benzenediol. Catechol is detected by the Pt/Au/RGO/GCE with a low detection limit in the presence of hydroquinone. [ABSTRACT FROM AUTHOR]

An enantioselective β-carbon amination for enals is disclosed. The nitrogen atom from a protected hydrazine with suitable electronic properties readily behaves as a nucleophile. Addition of the nitrogen nucleophile to a catalytically generated N-heterocyclic-carbene-bound α,β-unsaturated acyl azolium intermediate constructs a new carbon-nitrogen bond asymmetrically. The pyrazolidinone products from our catalytic reactions are common scaffolds in bioactive molecules, and can be easily transformed into useful compounds such as β3-amino-acid derivatives. [ABSTRACT FROM AUTHOR]

In 2011, a wilt disease has been detected on carnation ( Dianthus caryophyllus L.) cultivar ' Light Pink Barbara' in Kunming, Yunnan, China. A Fusarium sp. was consistently recovered from pieces of symptomatic tissues on Petri dishes containing potato dextrose agar ( PDA). On the basis of morphological characteristics and molecular identification by DNA sequencing of ribosomal DNA internal transcribed spacer (r DNA ITS) and partial translation elongation factor-1α ( TEF) gene region, following their phylogenetic trees construction, the putative causal agent was identified as Fusarium proliferatum ( Matsushima) Nirenberg, and its pathogenicity was finally confirmed by Koch's postulates. To our knowledge, this is the first report of a wilt disease caused by F. proliferatum on carnation in China. [ABSTRACT FROM AUTHOR]

An approach to highly functionalized donor-acceptor aziridines by the aziridination of N-tosylimines and 2-bromomalonates in the presence of sodium hydride under mild conditions has been developed. The high-yielding reaction has a relatively broad scope and can be easily scaled up to the gram level. [ABSTRACT FROM AUTHOR]

Developing methods to directly transform C(sp3) −H bonds is crucial in synthetic chemistry due to their prevalence in various organic compounds. While conventional protocols have largely relied on transition metal catalysis, recent advancements in organocatalysis, particularly with radical NHC catalysis have sparked interest in the direct functionalization of “inert” C(sp3) −H bonds for cross C−C coupling with carbonyl moieties. This strategy involves selective cleavage of C(sp3) −H bonds to generate key carbon radicals, often achieved via hydrogen atom transfer (HAT) processes. By leveraging the bond dissociation energy (BDE) and polarity effects, HAT enables the rapid functionalization of diverse C(sp3)−H substrates, such as ethers, amines, and alkanes. This mini‐review summarizes the progress in carbene organocatalytic functionalization of inert C(sp3)−H bonds enabled by HAT processes, categorizing them into two sections: 1) C−H functionalization involving acyl azolium intermediates; and 2) functionalization of C−H bonds via reductive Breslow intermediates. [ABSTRACT FROM AUTHOR]

The simple and environmentally friendly protocol proceeds with inexpensive reagents. [ABSTRACT FROM AUTHOR]

A graphical abstract of the article "Rapid Access to Bicyclic δ-Lactones via Carbene-Catalyzed Activation and Cascade Reaction of Unsaturated Carboxylic Esters" is presented.

The wide substrate scope, excellent yield, simple operating and purification procedures are advantages of the described method. [ABSTRACT FROM AUTHOR]

Lewis acid catalyzed ring-opening of donor-acceptor substituted aziridines is followed by 1,3-dipolar cycloaddition of the resulting azomethine ylides. [ABSTRACT FROM AUTHOR]