The C 2 -α-mannosyl-tryptophan amino acid is produced by a unique posttranslational modification (PTM) of proteins and poses a significant synthetic challenge. A new strategy based on Pd-catalyzed auxiliary-directed remote C-H glycosylation of tryptophan was developed, which generates the C 2 -α-mannopyranose (Man)-Trp unit in a highly efficient and stereoselective fashion. Density functional theory (DFT) computational studies support a concerted oxidative addition mechanism for the stereospecific functionalization of a Pd(II) palladacycle intermediate with an α-mannosyl chloride donor. The utility of this method was demonstrated in the first total synthesis of insect C-glycopeptide hormone Cam-HrTH-I.

A novel and efficient desymmetrizing asymmetric ortho-selective mono-bromination of bisphenol phosphine oxides under chiral squaramide catalysis was reported. Using this asymmetric ortho-bromination strategy, a wide range of chiral bisphenol phosphine...

Herein we report the catalytic asymmetric synthesis of a unique family of axially chiral enamides in good yields with excellent enantioselectivities under mild conditions. These new axially chiral compounds feature...