Catalytic transformation of alcohols via metal-catalyzed cross-coupling reactions is very important, but it typically relies on a multistep procedure. We here report a dynamic kinetic cross-coupling approach for the direct functionalization of alcohols. The feasibility of this strategy is demonstrated by a nickel-catalyzed cross-electrophile arylation reaction of benzyl alcohols with (hetero)­aryl electrophiles. The reaction proceeds with a broad substrate scope of both coupling partners. The electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)­aryl electrophiles (e.g., Ar–OTf, Ar–I, Ar–Br, and inert Ar–Cl) all coupled well. Most of the functionalities, including aldehyde, ketone, amide, ester, nitrile, sulfone, furan, thiophene, benzothiophene, pyridine, quinolone, Ar–SiMe3, Ar–Bpin, and Ar–SnBu3, were tolerated. The dynamic nature of this method enables the direct arylation of benzylic alcohol in the presence of various nucleophilic groups, including nonactivated primary/secondary/tertiary alcohols, phenols, and free indoles. It thus offers a robust alternative to existing methods for the precise construction of diarylmethanes. The synthetic utility of the method was demonstrated by a concise synthesis of biologically active molecules and by its application to peptide modification and conjugation. Preliminary mechanistic studies revealed that the reaction of in situ formed benzyl oxalates with nickel, possibly via a radical process, is an initial step in the reaction with aryl electrophiles.

Enantioselective cross-electrophile reactions remain a challenging subject in metal catalysis, and with respect to data, studies have mainly focused on stereoconvergent reactions of racemic alkyl electrophiles. Here, we report an enantioselective cross-electrophile aryl-alkenylation reaction of unactivated alkenes. This method provides access to a number of biologically important chiral molecules such as dihydrobenzofurans, indolines, and indanes. The incorporated alkenyl group is suitable for further reactions that can lead to an increase in molecular diversity and complexity. The reaction proceeds under mild conditions at room temperature, and an easily accessible chiral pyrox ligand is used to afford products with high enantioselectivity. The synthetic utility of this method is demonstrated by enabling the modification of complex molecules such as peptides, indometacin, and steroids.

The cross-electrophile coupling has become a powerful tool for C À C bond formation, but its potential for forging the C À Si bond remains unexplored. Here we report a crosselectrophile Csp 2-Si coupling reaction of vinyl/aryl electrophiles with vinyl chlorosilanes. This new protocol offers an approach for facile and precise synthesis of organosilanes with high molecular diversity and complexity from readily available materials. The reaction proceeds under mild and non-basic conditions, demonstrating a high step economy, broad substrate scope, wide functionality tolerance, and easy scalability. The synthetic utility of the method is shown by its efficient accessing of silicon bioisosteres, the design of new BCBmonomers, and studies on the Hiyama cross-coupling of vinylsilane products. Scheme 1. Transition metal-catalyzed cross-electrophile couplings. Scheme 2. Transition metal-catalyzed Csp 2-Si cross-coupling reactions.

In this study, the triblock copolymer poly(methyl methacrylate)-b-poly(butyl acrylate)-b-poly(methyl methacrylate) (MAM) was used to modify bisphenol A epoxy resin to improve its toughness.