Organic & Biomolecular Chemistry最新文献

A facile Zinc(II)-catalyzed cascade [4 + 2] cyclization of enynones with anthranils was developed to afford a series of 2-furanyl quinolines derivatives with various substituents in up to 91% yield via ring-opening/tandem cyclization. Mechanistic studies indicated that enaminone is an important intermediate, and furylcarbene was employed as a novel 2C synthon unit in this reaction. This protocol is characterized by high step economy, good functional group tolerance, simple operation, and a cheap zinc salt as the catalyst with low toxicity, and provides a new route for the synthesis of 2-furanyl quinolines with a variety of potential biomedical activities.

Antiapoptotic proteins represent a major obstacle to the success of anticancer therapies, as they promote the survival of malignant cells and contribute to treatment resistance. Among these, Bcl-2 and Bcl-xl are frequently overexpressed in pancreatic cancer, making them important therapeutic targets. In this work, we present a systematic computational study aimed at identifying the molecular features that enable selected cinnamyl and quinoxaline derivatives to inhibit the oligomerization of these proteins. Using a combination of molecular docking and molecular dynamics simulations, we characterized the most plausible binding modes and assessed the stability of the resulting complexes. Key intermolecular interactions responsible for binding were analyzed using the Quantum Theory of Atoms in Molecules (QTAIM), while reactivity descriptors derived from temperature-dependent chemical reactivity theory were employed to rationalize trends in affinity and stability. Our results reveal consistent structural and electronic patterns that govern the effective inhibition of Bcl-2 and Bcl-xl, providing mechanistic insight into their molecular recognition processes. Beyond improving the understanding of antiapoptotic protein inhibition, this study offers practical guidelines for the rational design of new small-molecule inhibitors with potential anticancer activity.

Electrochemical olefination has emerged as a fascinating alternative to classical phosphorus based and stoichiometric oxidant dependent methods for constructing carbon-carbon double bonds. This review comprehensively examines electrochemical strategies for alkene synthesis, including anodic oxidation, cathodic reduction, and hybrid metalla-electrocatalytic approaches. It discusses mechanistic insights involving radical and organometallic intermediates, evaluates functional-group tolerance in structurally complex substrates, and highlights recent technological advances and emerging applications in asymmetric synthesis and pharmaceutical derivatization. We evaluate catalytic systems featuring metal-free as well as palladium, rhodium, nickel, and cobalt catalyzed/mediated synthetic strategies across diverse molecular scaffolds. Strategic integration with renewable electricity infrastructure and complementary activation modes including photocatalysis positions electrochemical olefination as an indispensable component of contemporary sustainable synthesis across academic and industrial protocols.

We disclose a gold-catalyzed conversion of unactivated β-ketopropargyl amines to polysubstituted pyrroles under mild, operationally simple conditions. A broad substituent survey reveals clear structure-reactivity trends. With application of the revealed protocol, leveraging the propargyl tolerance, combining AuCI₃ with TBACN telescopes the sequence to a bicyclic indolizine ring.

Herein, we report a concise and efficient one-pot total synthesis of TMC-205 in 77% overall yield (gram-scale) using only two simple and streamlined steps. In the proposed approach, a novel Heck-dehydration reaction and a practical aromatic carboxylic acid introduction strategy are reported, which are characterized by high atom economy, excellent regioselectivity and stereoselectivity (E-isomer). This synthesis protocol is protecting group-free, redox neutral, environmentally benign, and features simple operation steps. Through the implementation of this new, efficient and scalable synthesis method, the formal synthesis of a series of novel meroterpenoid natural products can be successfully realized. Moreover, the synthetic strategy and methodologies demonstrated in this paper are useful and can be easily extended to the preparation of other related biologically active molecules.

A transition metal-free, iodine-catalyzed approach has been devised for the regioselective synthesis of diversely substituted 2-arylquinolines, benzo[h]quinolines, and pyrido[2,3-c]carbazole derivatives using β-chlorovinyl aldehydes as templates. The strategy has been found to be amenable to gram-scale synthesis, and its scope has been demonstrated with a library of 53 compounds with yields up to 95%. Operational simplicity, wide substrate scope, readily available starting materials, high efficiency, short reaction times, excellent yields, and metal-free conditions are the significant advantages offered by this strategy. The photophysical properties of all quinoline derivatives were also investigated, and excellent photophysical results were obtained with quantum yields (Φ_F) up to 36%.

N-Acyl amino acids are very important industrial surfactants, being gentle on the skin and completely biodegradable. The synthetic routes described in the literature involve the use of highly reactive acid chlorides or harsh reaction conditions. Following the latest trends in sustainable chemistry, in this work we developed an efficient, chemoselective, and environmentally friendly method for their synthesis, which involves the use of non-toxic enzymes as catalysts. Determining the most suitable starting materials and reaction conditions made it possible to achieve 97% product formation under mild reaction conditions.

Correction for 'Modular and chromatography-free synthesis of natural linear polyamines' by Masato Takahashi et al., Org. Biomol. Chem., 2026, 24, 675-680, https://doi.org/10.1039/D5OB01807B.

Herein, we report a new catalytic strategy for the efficient construction of indolo-oxazepine heterocycles. The transformation features a dirhodium carboxylate/Brønsted acid co-catalyzed [4 + 3] annulation between diazoenals and 3-substituted 2-oxindoles, providing direct access to valuable [1,3]oxazepino[3,2-a]indole derivatives. The synthetic utility of the methodology was demonstrated by a short synthesis of the indolo-oxazepane framework of a 5-HT₄ receptor antagonist, highlighting its potential utility in medicinal chemistry.

Helical aromatic oligoamides were synthesized via a polymerization strategy from amino acid-derived monomers to probe side-chain steric effects on helical chirality. Circular dichroism revealed tunable, reversible helicity dictated by substituent bulk. This work establishes tubular oligoamides as structurally precise yet responsive foldamers, enabling controlled chiroptical activity through targeted side-chain engineering.