Trends in Chemistry最新文献

The asymmetric partial reduction of substituted pyridines represents a direct and versatile strategy to access chiral di- and tetrahydropyridines, which are present in many natural products and active pharmaceutical ingredients (APIs). However, this methodology remains significantly underdeveloped when compared to the numerous exhaustive asymmetric reductions of pyridines to fully saturated piperidines, and is currently still limited to the synthesis of tetrahydropyridines. In this Opinion, we highlight the benefits, challenges, and current scope of asymmetric partial pyridine reductions, emphasizing prospective future directions to address significant gaps in the current literature.

DNA technology is rapidly expanding, with recent advances pushing functional DNA-based materials toward larger scales. Yet producing chemically modified DNA beyond the milligram-scale remains prohibitively expensive, challenging, and relatively unexplored limiting industrial and translational use. This feature review highlights emerging strategies for sourcing, modifying, and purifying DNA at scales relevant for materials and biotechnology. We compare bio-derived DNA sources (e.g., phage, plasmid, and genomic DNA) to conventional synthetic methods and examine their trade-offs. Critically, we re-examine recent and classic literature to identify chemical and enzymatic reactions practical for modifying bio-derived nucleic acids at relevant scales. Finally, we discuss scalable purification and characterization methods to support high-throughput workflows, enabling broader use of bio-derived dsDNA in next-generation applications.

Through mechanistic understanding, transition metal catalysis has evolved into a key component of organic chemists' toolbox. Improvements in ligand design continue to push the boundaries of applications beyond targeted synthesis. This forum contextualizes how mechanistic insight has influenced recent developments in transition metal-based molecular sensing.

Cells regulate responses to external stimuli and control cell fate through reversible modifications on proteins, DNA, and RNA typically introduced by enzymes. Next to these well-known enzymatically installed modifications, covalent modifications can also occur on these same biomolecules through spontaneous reaction with small molecules taken up from external sources or generated endogenously, e.g. byproducts of metabolic processes. These so-called non-enzymatic covalent modifications (NECMs) have been mainly studied on proteins and DNA, yet their biological role on RNA remains mostly underexplored. This review surveys identified and predicted RNA NECMs, explores their impact on RNA structure, stability, and function, and examines their potential link to diseases. Finally, we discuss regulation mechanisms of non-enzymatically modified RNAs and their potential significance on cellular dynamics.

BURP domain peptide cyclases, or BpCs (an abbreviation we recommend in this opinion), are an emerging class of copper enzymes which catalyze the oxidative macrocyclization of peptides in plants. A close examination of their novel protein fold, along with the unique dicopper active site that meticulously controls crosslinking within peptides, highlights how nature exploits intricate mechanistic strategies to achieve diverse functionalities. Here, we summarize recent discoveries regarding the sequence, structure, function, and proposed chemistry of BpCs. We also present plausible mechanistic ideas and recommend important structural considerations that could advance investigations and discussions surrounding their reactivity and underlying mechanisms.

1,3-Hydrogen (H) transfer of alkenes and alkynes has emerged as an atom-economic transformation in organic synthesis. The reaction usually takes place under mild conditions, avoids the need for external additives, and accommodates a broad range of functional groups. Although 1,3-H transfer was first realized a long time ago, only in recent times have there been more comprehensive and systematic studies on their enantiospecific transformations. This review summarizes the recent advances in enantiospecific 1,3-H transfer of alkenes and alkynes for the generation of centrally and axially chiral molecules. Examples where the enantiospecific 1,3-H transfer occurs inside a tandem reaction system are discussed. This review could inspire more studies on the development of enantiospecific 1,3-H transfer for asymmetric chemistry.