Chiral aldehyde catalysis opens new avenues for the activation of simple amines. However, the lack of easy access to structurally diverse chiral aldehyde catalysts has hampered the development of this cutting‐edge field. Herein, we report a Pd‐catalyzed atroposelective C−H naphthylation with 7‐oxabenzonorbornadienes for the preparation of axially chiral biaryls with excellent enantioselectivities (up to >99 % ee). This reaction is scalable and robust, which serves as a key step to provide a rapid access to axially chiral aldehyde catalysts through a three‐step C−H functionalization sequence. These chiral aldehydes exhibit better activities and enantioselectivities than the previously reported organocatalysts in the asymmetric activation of glycine derived amides and dipeptides. Moreover, preliminary investigation also discloses that the aldehyde catalyst can effectively override the intrinsic facial selectivity of chiral dipeptide substrates, showcasing the strong chiral induction ability of this type of novel aldehyde catalysts.

Biaryl atropisomers are of great importance in natural products,p harmaceuticals,a nd asymmteric synthesis. The efficient synthesis of these chiral scaffolds with full enantiocontrol and high diversity remains challenging. Reported herein is aP d-catalyzed atroposelective CÀH allylation with tert-leucine as an efficient catalytic chiral transient auxiliary.Awide range of enantioenriched biaryl aldehydes were prepared in synthetically useful yields with excellent enantioselectivity (up to > 99 %e e) through b-O elimination. The reaction could be carried out on agram scale without erosion of the ee value.Avariety of axially chiral carboxylic acids could be obtained with high enantiopurity. The resulting axially chiral biaryl aldehydes and carboxylic acids might be used in asymmetric synthesis as chiral ligands and/or organocatalysts.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

C-Glycosyl peptides/proteins are metabolically stable mimics of the native glycopeptides/proteins bearing O/N-glycosidic linkages, and are thus of great therapeutical potential. Herein, we disclose a protocol for the syntheses of vinyl C-glycosyl amino acids and peptides, employing a nickel-catalyzed reductive hydroglycosylation reaction of alkyne derivatives of amino acids and peptides with common glycosyl bromides. It accommodates a wide scope of the coupling partners, including complex oligosaccharide and peptide substrates. The resultant vinyl C-glycosyl amino acids and peptides, which bear common O/N-protecting groups, are amenable to further transformations, including elongation of the peptide and saccharide chains.

During the last two decades, impressive advancements have been achieved in transition metal-catalyzed chelation-assisted C-H functionalization reaction. While reactions in this field are still dominated by precious 4d or 5d metals (e.g., Pd, Rh, Ir), the 3d base metals (e.g., Ni, Co, Cu, Fe) have made significant headway partially due to their relatively large abundance, low cost, low toxicity as well as their occasionally occurred novel reactivity when compared to their noble cousins. This review will give a comprehensive summary on Ni-catalyzed functionalization of inert C-H bonds assisted by chelation groups. For clarity, the content is classified by the newly formed chemical bonds, namely C-C, C-N, C-chalcogen and C-halogen bond formation.Yan-Hua Liu (left) received his B.S. degree in 2013 from North University of China. Then he pursued his Ph.D. degree under the supervision of Prof. Bing-Feng Shi in organic chemistry at Zhejiang University. His current research is focused on transition-metal-catalyzed enantioselective C-H bond activation.