An enantioselective method for Pd(II)-catalyzed cross-coupling of methylene β-C(sp3)–H bonds in cyclobutanecarboxylic acid derivatives with arylboron reagents is described. High yields and enantioselectivities were achieved through the development of chiral mono-N-protected α-amino-O-methylhydroxamic acid (MPAHA) ligands, which form a chiral complex with the Pd(II) center. This reaction provides an alternative approach to the enantioselective synthesis of cyclobutanecarboxylates containing α-chiral quaternary stereocenters. This new class of chiral catalysts also show promises for enantioselective β-C(sp3)–H activation of acyclic amides.

A Pd(II)-catalyzed C-H phosphorylation reaction has been developed using heterocycle-directed ortho-palladation. Both H-phosphonates and diaryl phosphine oxides are suitable coupling partners for this reaction.

Significant progress has been made in the development of enantioselective C–H activation reactions via desymmetrization in the past decade. However, the requirement for the presence of two chemically identical prochiral C–H bonds represents an inherent limitation in scope. Here, we report the first example of kinetic resolution via Pd(II)-catalyzed enantioselective C–H activation and C–C bond formation, significantly expanding the scope of enantioselective C–H activation reactions.

Be dazzled by the sequence: The first efficient and general one‐pot method for the reductive bisalkylation of lactams/amides with Grignard and organolithium reagents has been developed (see scheme; DTBMP=2,6‐di‐tert‐butyl‐4‐methylpyridine, Tf=trifluoromethanesulfonyl).