In this paper, a visible-light-induced intramolecular [2+2] cycloaddition has been revealed to synthesize the bishomocubanone derivatives in moderate to excellent yield under mild conditions. This method demonstrated a broad substrate scope and excellent functional-group tolerance, affording cubane precursors and a series of bishomocubanones. Meanwhile, a hundred-gram scale experiment of this method has been employed to synthesize cubane precursors with 98% yield.

Chiral tertiary homoallylic alcohol and chiral alpha,alpha-disubstituted homoallylic amine scaffolds are ubiquitous in numerous bioactive natural products and pharmaceutically relevant molecules. Thus, asymmetric synthesis of these compounds has attracted an increasing attention from synthetic chemists. Compared to traditional methods, transition-metal-catalyzed asymmetric allylation of ketones or ketimines serves as a powerful methodology for constructing these compounds due to its excellent atom- and step-economy. Recent progress on copper(I)-catalyzed asymmetric allylation of ketones or ketimines is summarized. Based on the strategies for the generation of allyl-copper(I) species in situ, this review is divided into three sections: reactions through transmetalation, three-component coupling reactions, and proton-transfer reactions. The mechanisms and potential applications of some representative strategies are also included. Finally, the future developments in this field are outlooked.

Photosynthesis converts solar energy into chemical energy through highly coordinated photosynthetic reactions. Inspired by natural systems, artificial photosynthesis aims to develop an efficient, sustainable, and cost-effective pathway for solar-to-chemical conversion. This review examines natural photosynthetic pathways, including retinal/rhodopsin-, bacteriochlorophyll-, and chlorophyll-based systems, highlighting their key components and mechanisms. Next, we outline reaction pathways in artificial photosynthetic systems constructed via heterogeneous, homogeneous, self-assembly, and semi-artificial strategies, focusing on water splitting, carbon fixation, and nitrogen fixation. Finally, we offer insights into future directions for artificial photosynthesis, emphasizing the importance of using self-assembly strategies and the potential of using primitive phototrophic microorganisms as models.

Methods for direct enantioselective oxidation of C(sp3)-H bonds will revolutionize the preparation of chiral alcohols and their derivatives. Enzymatic catalysis, which uses key metal-oxo species to facilitate efficient hydrogen atom abstraction, has evolved as a highly selective approach for C-H oxidation in biological systems. Despite its effectiveness, reproducing this function and achieving high stereoselectivity in biomimetic catalysts has proven to be a daunting task. Here we present a copper-based biomimetic catalytic system that achieves highly efficient asymmetric sp3 C-H oxidation with C-H substrates as the limiting reagent. A Cu(II)-bound tert-butoxy radical is responsible for the site-selective C-H bond cleavage, which resembles the active site of copper-based enzymes for C-H oxidation. The developed method has been successfully accomplished with good functional group compatibility and exceptionally high site- and enantioselectivity, which is applicable for the late-stage oxidation of bioactive compounds.

Diphenylprolinol silyl ethers have been successfully identified as efficient chiral amines in the enantioselective allenation reaction of terminal alkynes and 2-alkynals. This reaction provides a diverse set of chiral allenynes with excellent enantioselectivity and decent yields. Furthermore, the current protocol is also compatible for the late-stage modification of some complex bioactive molecules, highlighting its potential in drug discovery.

The selective cleavage of C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 C double bonds to form carbonyl groups is a fundamental maneuver in retrosynthetic analysis, empowering swift alterations to molecular structures and efficient synthesis of sophisticated, multifunctional molecules. Traditional methods like ozonolysis are effective but come with safety, environmental, and economic challenges. To address these concerns, photochemical methods have recently emerged as ideal platforms for alkene oxidative cleavage through the utilization of photons as energy sources and open-shell radicals as reactive intermediates. Herein, we disclose an oxidant-free, operationally simple, and environmentally friendly protocol for the oxidative cleavage of cyclic alkenes via in situ-generated secondary alcohol intermediates. Facilitated by a bisphosphonium catalyst, the selective integration of alkoxy radical-mediated C-C bond scission with anti-Markovnikov alkene hydrofunctionalization led to the selective cleavage of cyclic alkenes and the formation of distal phenyl-substituted aldehydes with outstanding regioselectivity. This photocatalytic process accommodates both activated and unactivated cycloalkenes and operates under mild, redox-neutral conditions. Furthermore, the use of continuous-flow reactors has significantly improved photocatalytic efficiency, providing a robust and scalable solution for large-scale applications.

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization of inert C-H bonds, facilitating the use of nonprecious metal catalysts in demanding transformations. Notably, aerobic C-H carbonylation of methane to acetic acid remains formidable due to the rapid oxidation of methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT to achieve exceptional C2/C1 selectivity through synergistic photoexcitation, methyl radical generation, and carbonylation. Mechanistic studies highlight the critical roles of Fe(II) and Fe-carbonyl complexes in bypassing methyl radical oxidation via a radical rebound-like pathway, unlocking unprecedented efficiency in methane aerobic carbonylation.

Optimizing the morphology and vertical phase distribution of the active layers is crucial for organic solar cells (OSCs). This study introduces [6,6]-phenyl-C61-pentyl acrylate (PC61PeA), a cross-linkable acrylated-based fullerene acceptor (FA), as the third component in the PM6:BO-4Cl binary system. The PC61PeA functions as a morphology modulator, which enhances the aggregation of donor and acceptor species while facilitates the separation of BO-4Cl molecules. Additionally, the crosslinking of PC61PeA establishes highly conductive pathways within the bulk heterojunction (BHJ) layers, thereby significantly enhancing the diffusion length of charge carriers and improves charge transport in the BHJ blend. Multiple measurements confirm the accumulation of PC61PeA molecules at the BHJ/MoO3 and BHJ/ZnO interfaces. As a result, the PM6:BO-4Cl:PC61PeA inverted device achieves a notable power conversion efficiency of 18.43 %, surpassing the 16.14 % efficiency of the PM6: BO-4Cl binary device. Importantly, PC61PeA has a notable stabilizing effect on VOC and remarkably enhances the high-temperature (150 degrees C) thermal stability and UV-stability of OSCs.

The ever-increasing demand in chemical biology and medicinal research requires the development of new synthetic methods for the rapid construction of libraries of heterocycles from simple raw materials. In this context, the utilization of primary amines or H2O as the simple N- or O-sources in the assembly of a heterocyclic ring skeleton is highly desirable from the viewpoint of atom- and step-economy. Herein, we describe a highly efficient three-component reaction of diazo, allylic diacetates, and commercially available anilines (or H2O) to access structurally diverse pyrrolidine and tetrahydrofuran derivatives. This formal [1 + 1 + 3] annulation reaction features high efficiency, good yields, and broad functional group compatibility, making it a versatile and robust platform for the (formal) synthesis of several important bioactive molecules. Mechanistic studies suggested that the dirhodium-palladium bimetallic relay catalysis should play a key role in the successive steps of the current reaction, including sequential carbene insertion into the X-H bond and double allylic substitutions, thus allowing for building up molecular complexity from these simple raw materials.

Circadian neurons within animal brains orchestrate myriad physiological processes and behaviors, but the contribution of these neurons to the regulation of sleep is not well understood. To address this deficiency, we leveraged single-cell RNA sequencing to generate a comprehensive census of transcriptomic cell types of Drosophila clock neurons. We focused principally on the enigmatic DN3s, which constitute most fly brain clock neurons and were previously almost completely uncharacterized. These DN3s are organized into 12 clusters with unusual gene expression features compared to the more well-studied clock neurons. We further show that previously uncharacterized DN3 subtypes promote sleep through a G protein-coupled receptor, TrissinR. Our findings indicate an intricate regulation of sleep behavior by clock neurons and highlight their remarkable diversity in gene expression and functional properties.