Chemical Society Reviews最新文献

The field of directing group-assisted, transition-metal-catalyzed functionalization has undergone a significant transformation, evolving from the use of auxiliary group attachment for the exploitation of native functional groups in novel organic reactions. In particular, coordination-assisted C(sp³)–H bond functionalization has revolutionized synthetic planning to build molecular complexity. Recently, the use of native directing groups in transition-metal-catalyzed reactions has allowed a step-economic process for increased access to biologically important lactones and lactams. Accordingly, lactones and lactams are unavoidable structural motifs with widespread presence in many biological and pharmaceutical arenas, encouraging researchers to access and modify their structures for improved biological properties. In this review, we showcase the diverse aspects of transition metal catalysis, biocatalysis, and photocatalytic C(sp³)–H bond functionalization to access lactones and lactams assisted by carboxylic acid and amines/amides with auxiliary or transient directing groups or unique ligands. This article also emphasizes the role of specially designed complexes, artificial metalloenzymes, and biocatalysts in assembling lactones and lactams. Besides, three-component reactions involving CO as a C1 synthon play a vital role in developing these heterocycles. Importantly, the crucial role of ligands in determining regioselectivity and enhancing enantioselectivity is discussed thoroughly. For better clarity, this review is divided into twelve sections based on the catalysts involved, with subsections categorized by the type of bond activation or formation. Overall, this review aims to inspire the growth of C(sp³)–H bond functionalization, leading to the integration of lactams and lactones in organics.

The field of non-directed C–H activation, whether catalyzed by transition metals or carried out through metal-free methods, has emerged as a transformative strategy for functionalizing organic molecules. This contemporary approach creates new retrosynthetic disconnections and complements traditional methods that utilize directing groups, enabling the direct functionalization of arenes and heteroarenes without the need for these groups. This strategy enhances synthetic flexibility and creates distinct retrosynthetic pathways, thereby enriching established methodologies. This review covers the latest advancements in catalytic non-directed C(sp²)–H functionalization, with particular focus on both metal-catalyzed and metal-free systems. We examine notable progress in reaction scope, selectivity, and mechanistic insights, all of which highlight the strategic potential of these methods in the synthesis of complex molecules. Moreover, we discuss ongoing challenges, such as issues related to regioselectivity and substrate scope, while presenting potential avenues for improving the efficiency, sustainability, and applicability of non-directed C–H activation. The goal of this review is to provide a comprehensive picture of the current state of the field, aid understanding, and inspire further innovation in non-directed C–H functionalization as a versatile tool for advanced molecular design.

Low temperature aqueous electrochemical CO₍₂₎ reduction (ECR) emerged as a pathway to close the carbon cycle with the integration of renewable energy. However, activity, selectivity, and stability barriers prevent ECR from entering industrial scale operation. While catalyst design has made meaningful progress towards selective and active production of many products including CO, formate, and ethylene, operating conditions during catalyst testing have not been standardized. Operational parameters drastically impact the local reaction environment of the ECR and thus the performance of ECR. Herein, we summarize the prevailing operational variability of ECR and their interconnectedness. We first analyze reactant availability via tuning of cell geometry and CO₍₂₎ pressures. Then, optimization towards electrolyzer components including electrolyte, electrodes, and bipolar plates is discussed. We further assess the electrochemical protocols to enhance the performance or accelerate the degradation of ECR and the considerations required to scale up ECR to pilot scale. Finally, we provide perspectives on the current challenges of ECR and their promising solutions.

Antifreezing hydrogels have emerged as an innovative solution for maintaining functional performance and mechanical integrity in subzero environments, offering a robust alternative to traditional water-free antifreezing materials that often fail under wet and cold conditions. These water-rich hydrogels leverage their porous, crosslinked, polymeric networks, which serve as the structural basis for implementing two parallel strategies: the incorporation of antifreezing additives (peptides/proteins, salts, ionic liquids, and organics) and the meticulous engineering of polymer systems and network structures for manipulating the water–ice phase equilibrium to significantly enhance antifreezing properties. This review synthesizes recent findings to provide a fundamental overview of the important advancements in antifreezing hydrogels, focusing on their designs, mechanisms, performances, and functional applications. Various types of antifreezing hydrogels have been developed, utilizing strategies like the incorporation of antifreeze agents, use of strongly water-bound polymers, and design of highly crosslinked networks to illustrate different antifreezing mechanisms: freezing point depression, ice recrystallization inhibition, and network freezing inhibition. This review also explores the diverse functions of antifreezing hydrogels in biomedical devices, soft robotics, flexible electronics, food industry, and environmental engineering. Finally, this review concludes with future directions, emphasizing the potential of integrating machine learning and advanced molecular simulations into materials design. This strategic vision is aimed at promoting continuous innovation and progress in the rapidly evolving field of antifreezing hydrogels.

As the energy demands of the world continue to grow, the electroreduction of captured CO₂ (c-CO₂RR) is an appealing alternative to the traditional CO₂ reduction reaction (CO₂RR) as it does not include the energetically unfavorable release of CO₂ from the capture agent. In this tutorial we cover the motivation behind the c-CO₂RR and CO₂RR, their respective mechanisms, and computational tools that have been used to model these reactions and to compare their reactivities. Emphasis is given to methods that have already been used to model the c-CO₂RR but a comparison to the methods used to explore the more understood CO₂RR is covered as well.

The escalating global energy demands and the need to alleviate the rapid rise in greenhouse gases have led to colossal interest in designing efficient catalytic systems for photocatalytic CO₂ reduction. While inorganic semiconductors have been the frontrunners for a long time, porous photocatalysts, particularly covalent organic frameworks (COFs), are gaining traction due to their atomically precise structures, enabling tuning their structural and chemical properties. Designed using the principles of reticular chemistry, the building units of COFs can be modulated to incorporate catalytically active sites periodically using robust covalent bonds to endow them with high efficiency, selectivity, and stability. Unlike the non-porous congeners, COFs, with their high porosity and precisely defined pore channels, allow for quicker diffusion of substrates and products, enabling the utilization of deeply buried photocatalytic sites. Our approach is to comprehend the significant roadblocks that must be overcome for designing state-of-the-art catalysts for photocatalytic CO₂ reduction. Building upon that, we highlight the key strategies devised to design COF-based CO₂RR photocatalysts. A fundamental understanding of the structure–property relationship is quintessential for utilizing the precision of COF chemistry for developing next-generation materials combining activity, selectivity, and efficiency in a single system. Throughout this review, we have taken a closer look at how the critical design aspects and molecular engineering reciprocate towards augmenting the bulk photocatalytic properties of efficiency and selectivity. Understanding molecular engineering and structure–property relationships will be conducive to developing sophisticated systems to solve global crises in this burgeoning area of research.

Substituting CC double bonds with B–N bonds in polycyclic aromatic hydrocarbons (PAHs) has emerged as a promising approach to advance and diversify organic functional materials. This structural modification not only imparts unique electronic and optical properties, but also enhances chemical stability, thereby opening new avenues for material design and applications. However, the widespread adoption of BN-fused aromatic hydrocarbons in practical applications is still in its nascent phase. This constraint stems primarily from the challenges in precisely tailoring molecular structures to optimize photophysical and electronic properties, thereby influencing their efficacy in targeted applications. Consequently, a comprehensive evaluation of historical, current, and prospective developments in BN-fused aromatic hydrocarbons is deemed essential. This review offers an in-depth overview of recent advancements in BN-fused aromatic hydrocarbons, focusing on synthetic strategies, fundamental properties, and emerging applications. Additionally, we elucidate the pivotal role of computational chemistry in directing the design, discovery, and optimization of these materials. Our objective is to foster interdisciplinary collaboration and stimulate innovative approaches to fully harness the potential of azaborinine chemistry across various fields, including organic optoelectronics, biomedicine, and related disciplines.

Engineered lipid nanoparticles (LNPs) represent a breakthrough in targeted drug delivery, enabling precise spatiotemporal control essential to treat complex diseases such as cancer and genetic disorders. However, the complexity of the delivery process—spanning diverse targeting strategies and biological barriers—poses significant challenges to optimizing their design. To address these, this review introduces a multi-domain framework that dissects LNPs into four domains: structure, surface, payload, and environment. Engineering challenges, functional mechanisms, and characterization strategies are analyzed across each domain, along with a discussion of advantages, limitations, and in vivo fate (e.g., biodistribution and clearance). The framework also facilitates comparisons with natural exosomes and exploration of alternative administration routes, such as intranasal and intraocular delivery. We highlight current characterization techniques, such as cryo-TEM and multiscale molecular dynamics simulations, as well as the recently emerging artificial intelligence (AI) applications—ranging from LNP structure screening to the prospective use of generative models for de novo design beyond traditional experimental and simulation paradigms. Finally, we examine how engineered LNPs integrate active, passive, endogenous, and stimuli-responsive targeting mechanisms to achieve programmable delivery, potentially surpassing biological sophistication in therapeutic performance.

The Suzuki–Miyaura cross-coupling is a powerful method for carbon–carbon bond formation, widely applied with various substrates, catalysts, reagents and solvents. However, numerous reported protocols make finding optimal conditions for a specific substrate time-consuming. This tutorial review provides a comprehensive overview on recent developments in Suzuki–Miyaura reactions, focusing on optimizing the most common application: palladium and nickel phosphine catalyzed (hetero-)aryl bond formation. Key mechanistic insights into ligand selection, base and boron reagent choice as well as potential additives, and their effects on the reaction outcome are discussed in detail. Based on a systematic analysis, these parameters will be grouped together. Recommended conditions for each group will then be provided to accelerate the optimization process and enhance the application of this pivotal bond forming reaction.

Correction for ‘Electrochemical nitrogen fixation and utilization: theories, advanced catalyst materials and system design’ by Wenhan Guo et al., Chem. Soc. Rev., 2019, 48, 5658–5716, https://doi.org/10.1039/C9CS00159J.