A Rh(I)-catalyzed enantioselective C2-arylation of indole derivatives with aryl bromides is reported. In the presence of the Rh/chiral cyclohexyl-fused SPINOL-derived phosphoramidite complex, C2-arylation of indoles proceeded smoothly, affording a wide range of indole-C3 biaryl-type atropisomers in good yields and enantioselectivity (up to 98% yield, up to 92% ee) under mild conditions. This method displays good functional group tolerance.

Bisphosphine monoxides (BPMOs) represent a distinctive class of hemilabile bidentate ligands featuring a trivalent phosphine as a soft coordination site, combined with a hard coordination site in the form of P(v)O; hence, they are referred to as P,PO ligands. Despite their potential benefits, including their ability to regulate a variety of elementary steps essential in transition metal-enabled organic reactions, such as ligand exchange, isomerization, oxidative addition, migratory insertion, and reductive elimination, the P,PO ligands have not garnered significant attention compared with other hemilabile ligands and bidentate phosphine ligands in the past decades. This limited recognition is due to challenges associated with their synthesis methods and their inconspicuous presence within high-valent transition-metal/bidentate phosphine ligand catalytic systems under basic or oxygen-containing conditions. The incorporation of the P,PO ligands in transition metal-catalyzed organic reactions offers a pathway characterized by low activation energy for a diverse range of reactions. Herein, this review article provides a comprehensive overview of the utilization of the BPMO ligands in transition metal-catalyzed organic transformations from around 2004 to date, encompassing addition reactions, alkene functionalization reactions, coupling reactions, [4 + 2] cycloadditions, C-H functionalizations, and other transformations.

Harsh modern industrial working conditions require high-performance lubricants, but traditional additives are limited by single functionality and poor compatibility, driving the development of multifunctional alternatives. Two novel hindered phenolic amide-esters (MADE, DAME) were synthesized and characterized. Their thermal/storage stability, antioxidant and tribological properties in synthetic oil were evaluated, with commercial 1010 and T203 as references. DFT calculations and worn surface analysis were also employed to clarify the lubrication mechanism. The results indicate that MADE exhibits better thermal/storage stability, comprehensive antioxidation and lubricating performance than DAME, with residual mass of 85.3% and 73.2% at 300 degrees C, respectively. A total of 1 wt.% MADE shortens the running-in period to 200 s (vs. 300 s for base oil), reduces the average. WSD by 12.1% and wear volume by 60.2%. Mechanistically, MADE adsorbs strongly on metal surfaces and forms a protective tribofilm via tribochemical reaction, exhibiting synergistic antioxidant and anti-wear effects. This work establishes a novel and sustainable paradigm for developing next-generation, multifunctional lubricant additives with high performance.

Despite the widespread occurrence of enantiomerically enriched tertiary alcohols in bioactive molecules and pharmaceuticals, efficient methods for preparing optically pure alpha,beta-stereogenic tertiary alcohols remain scarce. Here, we report a dynamic kinetic asymmetric allylation of readily available racemic ketones with 2-aza-1,4-dienes. Notably, through the judicious selection of chiral ligands for copper catalysts, both E- and Z-isomers can be accessed with high efficiency and stereocontrol. Density functional theory (DFT) calculations reveal that ligand-controlled face-selective attacks via distinct allylcopper intermediates dictate the stereodivergent E/Z selectivity. This reaction achieves excellent diastereo- and enantioselectivity, accommodates a broad range of heterocyclic substrates, and exhibits extensive functional group tolerance. We demonstrate the utility of this protocol by modifying Profen-type drugs and rapidly synthesizing complex drug molecules. This study provides a versatile and efficient route to diverse chiral tertiary alcohols, offering a powerful tool for pharmaceutical assembly.