Enantioselective [2 + 2] Photocycloreversion Enables De Novo Deracemization Synthesis of Cyclobutanes.

While photochemical deracemization significantly enhances atom economy by eliminating the necessity for additional oxidants or reductants, the laborious presynthesis of substrates from feedstock chemicals is often required, thereby compromising the practicality of this method. In this study, we propose a novel approach known as de novo deracemization synthesis, which involves direct utilization of simple substrates undergoing both photochemical transformation and reversible photochemical transformation. The efficient enantiocontrol of chiral catalysts in the latter process establishes an effective platform for deracemization. This alternative and practical approach to address the challenges of asymmetric photocatalysis has been successfully demonstrated in the photosensitized de novo deracemization synthesis of azaarene-functionalized cyclobutanes featuring three stereocenters, including an all-carbon quaternary center. By exclusively employing a suitable chiral catalyst to enable kinetically controlled [2 + 2] photocycloreversion, we pave a creative path toward achieving more cost-effective photochemical deracemization.

Photoredox Catalytic Deracemization Enabled Enantioselective and Modular Access to Axially Chiral N-Arylquinazolinones.

Visible light-driven photocatalytic deracemization is highly esteemed as an ideal tool for organic synthesis due to its exceptional atom economy and synthetic efficiency. Consequently, successful instances of deracemization of allenes have been established, where the activated energy of photosensitizer should surpass that of the substrates, representing an intrinsic requirement. Accordingly, this method is not applicable for axially chiral molecules with significantly high triplet energies. In this study, we present a photoredox catalytic deracemization approach that enables the efficient synthesis of valuable yet challenging-to-access axially chiral 2-azaarene-functionalized quinazolinones. The substrate scope is extensive, allowing for both 3-axis and unmet 1-axis assembly through facile oxidation of diverse central chiral 2,3-dihydroquinazolin-4(1H)-ones that can be easily prepared and achieve enantiomer enrichment via deracemization. Mechanistic studies reveal the importance of photosensitizer selection in attaining excellent chemoselectivity and highlight the indispensability of a chiral Brønsted acid in enabling highly enantioselective protonation to accomplish efficient deracemization.

Preparation and Immobilization Mechanism on a Novel Composite Carrier PDA-CF/PUF to Improve Cells Immobilization and Xylitol Production.

The preparation of a novel composite carrier of polydopamine-modified carbon fiber/polyurethane foam (PDA-CF/PUF) was proposed to improve cell immobilization and the fermentation of xylitol, which is an important food sweetener and multifunctional food additive. Candida tropicalis was immobilized on the composite carrier by adsorption and covalent binding. The properties and immobilization mechanism of the composite carrier and its effect on immobilized cells were investigated. It showed that the modification of PDA enhanced the loading of CF on the PUF surface and the adhesion of cells on the composite carrier surface. Also, the biocompatibility of carriers to cells was improved. In addition, the introduction of PDA increased the active groups on the surface of the carrier, enhanced the hydrophilicity, promoted the cells immobilization, and increased the xylitol yield. It was also found that expression of the related gene XYL1 in cells was significantly increased after the immobilization of the PDA-CF/PUF composite carrier during the fermentation. The PDA-CF/PUF was an immobilized carrier with the excellent biocompatibility and immobilization performance, which has great development potential in the industrial production of xylitol.

Visible light-driven dearomative ring expansion of (aza)arenes to access dihydrofuran-based polycyclic compounds.

The dearomative expansion of aromatic rings has long been pursued by chemists due to its potential to provide tractable approaches for synthesizing valuable non-aromatic molecules. To circumvent the conventional use of hazardous and unstable diazo compounds, photochemical synthesis has recently emerged as a promising platform. However, protocols that can effectively handle both arenes and azaarenes remain scarce. Herein, we introduce a generic strategy that efficiently converts ß-(aza)aryl-ß-substituted enones into biologically significant cycloheptatriene derivatives, including their aza-variants. This method allows for the easy modulation of diverse functional groups on the product and demonstrates a wide substrate scope, evidenced by its excellent tolerance to various drug motifs and good compatibility with five-membered azaarenes undergoing ring expansion. Moreover, DFT calculations of plausible mechanisms have motivated the implementation of an important cascade diradical recombination strategy for 1,3-dienones, thus facilitating the synthesis of valuable 2-oxabicyclo[3.1.0]hex-3-ene derivatives.

Enantioselective Hydroaminoalkylation of Azaaryl Ketones through Asymmetric Photoredox Catalysis.

An enantioselective hydroaminoalkylation of azaaryl ketones under a transition-metal-free asymmetric photoredox catalysis platform is reported. A series of valuable azaarene-functionalized 1,2-amino alcohols featuring attractive quaternary carbon stereocenters have been synthesized in high yields with good to excellent enantioselectivities. The viability of readily accessible N-aryl glycines as reaction partners facilitates the conjugate modification of these products into important derivatives, thereby enhancing the synthetic utility of the current approach.

Research progress on biosynthesis of erythritol and multi-dimensional optimization of production strategies.

Erythritol, as a new type of natural sweetener, has been widely used in food, medical, cosmetics, pharmaceutical and other fields due to its unique physical and chemical properties and physiological functions. In recent years, with the continuous development of strategies such as synthetic biology, metabolic engineering, omics-based systems biology and high-throughput screening technology, people's understanding of the erythritol biosynthesis pathway has gradually deepened, and microbial cell factories with independent modification capabilities have been successfully constructed. In this review, the cheap feedstocks for erythritol synthesis are introduced in detail, the environmental factors affecting the synthesis of erythritol and its regulatory mechanism are described, and the tools and strategies of metabolic engineering involved in erythritol synthesis are summarized. In addition, the study of erythritol derivatives is helpful in expanding its application field. Finally, the challenges that hinder the effective production of erythritol are discussed, which lay a foundation for the green, efficient and sustainable production of erythritol in the future and breaking through the bottleneck of production.

Catalytic asymmetric [4 + 2] dearomative photocycloadditions of anthracene and its derivatives with alkenylazaarenes.

Photocatalysis through energy transfer has been investigated for the facilitation of [4 + 2] cycloaddition reactions. However, the high reactivity of radical species poses a challenging obstacle to achieving enantiocontrol with chiral catalysts, as no enantioselective examples have been reported thus far. Here, we present the development of catalytic asymmetric [4 + 2] dearomative photocycloaddition involving anthracene and its derivatives with alkenylazaarenes. This accomplishment is achieved by utilizing a cooperative photosensitizer and chiral Brønsted acid catalysis platform. Importantly, this process enables the activation of anthracene substrates through energy transfer from triplet DPZ, thereby initiating a precise and stereoselective sequential transformation. The significance of our work is highlighted by the synthesis of a diverse range of pharmaceutical valuable cycloadducts incorporating attractive azaarenes, all obtained with high yields, ees, and drs. The broad substrate scope is further underscored by successful construction of all-carbon quaternary stereocenters and diverse adjacent stereocenters.

Asymmetric photoredox catalytic formal de Mayo reaction enabled by sensitization-initiated electron transfer.

Visible-light-driven photoredox catalysis is known to be a powerful tool for organic synthesis. Its occurrence critically depends on the twice exothermic single-electron transfer processes of photosensitizers, which are governed by the redox properties of the species involved. Hence, the inherently narrow range of redox potentials of photosensitizers inevitably constrains their further availability. Sensitization-initiated electron transfer has recently been found to effectively overcome this substantial challenge. However, feasible and practical strategies for designing such complicated catalytic systems are rather scarce. Herein we report an elaborate dual-catalyst platform, with dicyanopyrazine as a visible light photosensitizer and a pyrenyl-incorporated chiral phosphoric acid as a co-sensitizer, and we demonstrate the applicability of this sensitization-initiated electron transfer strategy in an asymmetric formal de Mayo-type reaction. The catalysis platform enables otherwise thermodynamically unfavourable electron transfer processes to close the redox cycle and allows for precise access to valuable enantioenriched 1,5-diketones with a wide substrate range.

[Research progress on pathogenic mechanism of sepsis-induced liver injury and treatment with traditional Chinese medicine and its active components].

Sepsis is a systemic inflammatory response syndrome caused by infection, with high morbidity and mortality. Sepsis-induced liver injury(SILI) is one of the manifestations of sepsis-induced multiple organ syndrome. At present, there is no recommended pharmacological intervention for the treatment of SILI. traditional Chinese medicine(TCM), based on the holism and dialectical treatment concept, shows the therapeutic characteristics of multi-target and multi-pathway and can comprehensively prevent and treat SILI by interfering with inflammatory factors, inflammatory signaling pathways, and anti-oxidative stress and inhibiting apoptosis. This article reviewed the experimental studies on the treatment of SILI with TCM to clarify its pathogenic mechanism and therapeutic characteristics, so as to provide more ideas and directions for the development or preparation of new drugs.

Radical Cross Coupling and Enantioselective Protonation through Asymmetric Photoredox Catalysis.

An unprecedented enantioselective protonation reaction enabled by photoredox catalytic radical coupling is developed. Under cooperative dicynopyrazine-derived chromophore (DPZ) as a photosensitizer and a chiral phosphoric acid catalyst, and Hantzsch ester as a sacrificial reductant, the transformations between α-substituted enones and cyanoazaarenes or 2-(chloromethyl)azaaren-1-iums can proceed a tandem reduction, radical coupling, and enantioselective protonation process efficiently. Two classes of pharmaceutically important enantioenriched azaarene variants, which contain a synthetically versatile ketone-substituted tertiary carbon stereocenter at the ß- or γ-position of the azaarenes, are synthesized with high yields and ees.