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).
Pd(II)-catalyzed arylation of γ-C(sp3)–H bond of aliphatic acid-derived amides is developed by using quinoline-based ligands. Various γ-aryl-α-amino acids are prepared from natural amino acids using this method. The influence of ligand structure on reactivity is also systematically investigated.
A Pd(II)-catalyzed enantioselective C–H cross-coupling of benzylamines via kinetic resolution has been achieved using chiral mono-N-protected α-amino-O-methylhydroxamic acid (MPAHA) ligands. Both chiral benzylamines and ortho-arylated benzylamines are obtained in high enantiomeric purity. The use of a readily removable nosyl (Ns) protected amino group as the directing group is a crucial practical advantage. Moreover, the ortho-arylated benzylamine products could be further transformed into chiral 6-substituted 5,6-dihydrophenanthridines as important structural motifs in natural products and bioactive molecules.
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