A gold(I)-catalyzed regioselective cycloisomerization of bis(indol-3-yl)-ynamides for the rapid construction of five-membered ring linked bisindole derivatives has been reported, affording the desired products in the range of 72%-94% yields under mild conditions along with broad substrate scope. Moreover, DFT calculation of the NBO (natural bond orbital) charge supports the origin of its regioselectivity.

Herein, a copper(I)-catalyzed asymmetric 1,4-hydroarsination of beta-substituted alpha,beta-unsaturated esters is achieved in moderate to excellent yields with high to excellent enantioselectivity, based on the proposed nucleophilic [Cu]-AsPh2 species. As for alpha-substituted alpha,beta-unsaturated esters, a 1,4-hydroarsination/enantioselective protonation event occurs smoothly in satisfying results. Furthermore, beta-substituted alpha,beta-unsaturated ketone, alpha,beta-unsaturated amide, and alpha,beta-unsaturated phosphine sulfide are well applied in the present catalytic system. Finally, some control experiments show that HAsPh2 is activated through coordination with the copper(I) catalyst and HAsPh2 exhibits inferior soft Lewis basicity to HPPh2 in the presence of a copper(I)-bisphosphine complex.

Sodium oligomannate, a sophisticated mixture of acidic linear beta-(1,4)-d-oligomannurarate ranging from dimers to decamers with an average molecular weight of 670 similar to 880 Da, has gained conditional approval for the treatment of Alzheimer's disease. Herein, we develop an efficient approach to the chemical synthesis of well-defined beta-(1,4)-d-mannurarate di-, tetra-, hexa- and octasaccharides (1-4), utilizing N-phenyl trifluoroacetimidate donors and thioglycoside acceptors for the stereoselective assembly of the desired beta-(1,4)-d-mannuronate linkages. This approach features a straightforward protecting group strategy with only two types of protecting groups: tert-butyldimethylsilyl (TBS) for the 4-OH at the non-reducing end and benzyl (Bn) for free hydroxyl and carboxylic acid moieties, thereby ensuring the stereoselective formation of the beta-mannosyl bonds and facilitating sequential transformation into the target beta-(1,4)-d-mannurarate oligosaccharides. The scalability of the present synthesis of these oligosaccharides paves the way for in-depth structure-activity relationship studies and pharmacological investigations of sodium oligomannates.

Chiral gamma-amino alcohols are prevalent structural motifs in natural products and bioactive compounds. Nevertheless, efficient and atom-economical synthetic methods toward enantiomerically enriched gamma-amino alcohols are still lacking. In this study, a highly enantioselective rhodium-catalyzed reductive hydroformylation of readily available alpha-substituted enamides is developed, providing a series of pharmaceutically valuable chiral 1,3-amino alcohols in good yields and excellent enantioselectivities in a single step. The development of the 4,4 '-bisarylamino-substituted BIBOP ligand is crucial for the success of this transformation. DFT calculations and experimental data have revealed the importance of hydrogen bonding between the N-H group in the structure of TFPNH-BIBOP and the enamide carbonyl group in promoting both high enantioselectivity and reactivity. This method has enabled the concise synthesis of several chiral pharmaceutical intermediates including a single-step synthesis of the key chiral intermediate of maraviroc.

Numerous metallo-supramolecules with well-defined sizes and shapes have been successfully constructed via the strong coordination interaction between terpyridine (TPY) moieties and ruthenium cations. However, the pseudo-octahedral geometry of unit hampers the luminescent properties of such metallo-architectures, thus limiting their applications as optical materials. To address this issue, we herein use a flexible alkyl chain to bridge TPY building blocks, replacing conventional linkage. The introduction of alkyl chain guides the self-assembly into desired architecture while simultaneously eliminating the quenching effects typically associated with the linkage. More importantly, this design strategy enables the precise construction of bowtie-shaped metallo-supramolecules with significantly enhanced emission. The incorporation of alkyl chain linkage not only maintains structural integrity but also enhances optical performance, making these metallo-supramolecular assemblies highly promising for applications in advanced photonic and luminescent materials. This study offers a versatile approach to construct complex metallo-supramolecular architectures with desired optical properties.