Modular type I polyketide synthases (PKSs) are remarkable molecular machines that can synthesize structurally complex polyketide natural products with a wide range of biological activities. In these molecular machines, ketosynthase (KS) domains play a central role, typically by catalyzing decarboxylative Claisen condensation for polyketide chain extension. Noncanonical KS domains with catalytic functions rather than Claisen condensation have increasingly been evidenced, further demonstrating the capability of type I PKSs for structural diversity. This review provides an overview of the reactions involving unusual KS activities, including PKS priming, acyl transfer, Dieckmann condensation, Michael addition, aldol-lactonization bicyclization, C-N bond formation and decarbonylation. Insights into these reactions can deepen the understanding of PKS-based assembly line chemistry and guide the efforts for rational engineering of polyketide-related molecules.

Organic phosphorescent materials have great prospects for application, whose performance particularly depends on the preparation method. Inspired by nature's wisdom, we report a phosphor that can utilize monomers in its environment by polymerization to construct a rigid microenvironment under light illumination, leading to a glow-in-the-dark emulsion with a phosphorescence lifetime of 1 s in water. This phosphor can achieve active growth of the aqueous emulsion with the introduction of more monomers. In the presence of trace amounts of oxygen (which has adverse effects on both polymerization and afterglow), this phosphor can still undergo photo-induced polymerization, removing the influence of oxygen and obtaining afterglow emulsion, demonstrating its adaptability to the environment. This phosphor can also catalyze the polymerization of monomers containing yellow fluorophore, obtaining long-lifetime yellow afterglow emulsion through excited state energy transfer. We have also conducted in-depth studies on the photo-catalytic and phosphorescent properties of this phosphor in model systems. This biomimetic intelligent manufacturing provides a new approach for organic phosphorescent materials and is significant for future applications. Organic afterglow materials show great potential in diverse applications, and their performance particularly depends on their method of preparation. Here, the authors report a biomimetic phosphor that builds a rigid microenvironment to restrain non-radiative decay of triplet excitons, achieving long-lived organic afterglow in water.

Real-time monitoring of molecular transformations is crucial for advancements in biotechnology. In this study, we introduce a novel self-assembling 19F-labeled nuclear magnetic resonance (NMR) probe that disassembles upon interaction with various nucleotides. This interaction not only activates the 19F signals but also produces distinct signatures for each specific component, thereby enabling precise identification and quantification of molecules in evolving samples. We demonstrate the capability of this probe for real-time monitoring of adenosine triphosphate (ATP) hydrolysis and screening potential enzyme inhibitors. These applications highlight the probe's significant potential in enzyme analysis, drug development, and disease diagnostics.

Phosphine-mediated reactions driven by the formation of phosphine oxide have long been recognized as an intriguing approach in forming C--C, C--N, and C-X (where X represents O, N, S etc.) bonds. In the field of P (III)/P(V)=O redox catalysis, the asymmetric version is still in its infancy. In the past decade, several noteworthy works on asymmetric P(III)/P(V)=O redox catalysis processes revealed their application in various chemically valuable transformations. These achievements also elucidated unique features of catalyst structures for catalyst design. In this review, we will delve into these advances, with a specific emphasis on the phosphine skeletons used and the reduction conditions employed, providing future directions in the development of asymmetric P (III)/P(V)=O redox catalysis.

Selective C-F bond activation through a radical pathway in the presence of multiple C-H bonds remains a formidable challenge, owing to the extraordinarily strong bond strength of the C-F bond. By the aid of density functional theory calculations, we disclose an innovative concerted electron-fluoride transfer mechanism, harnessing the unique reactivity of Lewis base-boryl radicals to selectively activate the resilient C-F bonds in fluoroalkanes. This enables the direct abstraction of a fluorine atom and subsequent generation of an alkyl radical, thus expanding the boundaries of halogen atom transfer reactions.

Significant strides have been made in synthetic chemistry concerning icosahedral boron clusters over the past decades, resulting in a proliferation of applications across various research domains including weakly coordinating anions, supramolecular chemistry, medicinal chemistry, catalysis, porous materials, and more. However, compared to neutral counterpart carboranes C 2 B 10 H 12 , the synthetic chemistry of [B 12 H 12 ] 2- and [CB11H12]- clusters remains comparatively underexplored and lacks systematic discussion, impeding further advancement. This review aims to consolidate the current progress in the synthetic chemistry of closo-dodecaborate (2-) [B 12 H 12 ] 2- and carba-closo-dodecaborate(-) [CB11H12]- anions, elucidate effective strategies for vertex modification, and scrutinize pertinent challenges in real- world preparation. Accordingly, we present a comprehensive analysis of icosahedral boron cluster anion functionalization based on reaction mechanisms. The reaction mechanism of [B 12 H 12 ] 2- encompasses eight primary categories: electrophilic substitution, acid-catalyzed nucleophilic substitution, radical reactions, transition metal catalyzed cross-coupling, transition metal catalyzed B-H activation, organocatalyzed B-H activation, microwave-promoted reactions, and other reactions occurring under special conditions or with unknown mechanisms. Similarly, the reaction pathways for [CB11H12]- can be initially categorized into two types based on substitutions at carbon or boron vertices. Carbon vertex derivations are further dissected into four parts: electrophilic substitution, nucleophilic substitution, radical reactions, and transition metal catalyzed cross-coupling, while boron vertex modifications are similarly divided into electrophilic substitution, nucleophilic substitution, radical reactions, transition metal catalyzed cross-coupling, and transition metal catalyzed direct B-H activation. Electrophilic substitutions at boron vertices encompass various reactions including deuteration, mercuriation, hydroxylation, halogenation, and alkylation. Besides, we also discuss the applications of [B 12 H 12 ] 2- and [CB11H12]- derivatives. In the concluding section, we offer recommendations for further advancements in anionic boron cluster research. This comprehensive review serves as a valuable resource for researchers seeking to develop more efficient methodologies for functionalizing anionic boron cluster compounds. Many of the outlined synthetic methodologies hold potential for application in other cage boron anions such as [B 10 H 10 ] 2- , [CB9H10]-, and metallacarboranes. We anticipate that continued progress in synthetic chemistry will unveil novel applications based on [B 12 H 12 ] 2- and [CB11H12]- clusters.

A simple and highly efficient method for the double O-difluoromethylations of diphenols in 10 min is described, using TMSCF2Br as a difluorocarbene reagent. The reactivity order of different diphenols is o-diphenol > m- diphenol > p-diphenol in the two-phase difluoromethylation reaction, which can be explained by the different lipophilicities of these different diphenols.

Metal migration strategy can offer BH functionalization of o-carboranes at different positions from where initial bond activation occurs to achieve bifunctionalized o-carboranes in one reaction. We report in this article an enantioselective 3,4-bifunctionalization of o-carboranes via asymmetric Pd migration with a high efficiency and up to 98 % ee. This asymmetric catalysis has a broad substrates scope, leading to the preparation of a class of chiral-at-cage o-carborane derivatives. The enantiocontrol model is suggested on the basis of density functional theory (DFT) results, where the chiral Trost ligand plays a crucial role in this enantioselective Pd migration from exo-alkenyl sp2 C to the cage B(4) position of o-carborane.

Pseudokinase TRIB2, a member of the CAMK Ser/Thr protein kinase family, regulates various cellular processes through phosphorylation-independent mechanisms. Dysregulation of TRIB2 has been implicated in promoting tumor growth, metastasis, and therapy resistance, making it a promising target for cancer treatment. In this study, we designed and synthesized a series of TRIB2 PROTAC degraders by conjugating a TRIB2 binder 1 with VHL or CRBN ligands via linkers of varying lengths and compositions. Among these compounds, 5k demonstrated potent TRIB2 degradation with a DC50 value of 16.84 nM (95 % CI: 13.66-20.64 nM) in prostate cancer PC3 cells. Mechanistic studies revealed that 5k directly interacted with TRIB2, selectively inducing its degradation through a CRBN-dependent ubiquitin-proteasomal pathway. Moreover, 5k outperformed the TRIB2 binder alone in inhibiting cell proliferation and inducing apoptosis, confirming that TRIB2 protein degradation could be a promising therapeutic strategy for TRIB2-associated cancers. Additionally, compound 5k also serves as an effective tool for probing TRIB2 biology.