Ru(II)-catalyzed enantioselective C−H functionalization involving an enantiodetermining C−H cleavage step remains undeveloped. Here we describe a Ru(II)-catalyzed enantioselective C−H activation/annulation of sulfoximines with αcarbonyl sulfoxonium ylides using a novel class of chiral binaphthyl monocarboxylic acids as chiral ligands, which can be easily and modularly prepared from 1,1′-binaphthyl-2,2′-dicarboxylic acid. A broad range of sulfur-stereogenic sulfoximines were prepared in high yields with excellent enantioselectivities (up to 99% yield and 99% ee) via desymmetrization, kinetic resolution, and parallel kinetic resolution. Furthermore, the resolution products can be easily transformed to chiral sulfoxides and key intermediates for kinase inhibitors.

Transition-metal-catalyzed asymmetric C–H activation reactions generally rely on the design of ligands with sterically bulky groups to create a chiral environment for enantioinduction through steric repulsion. Here we describe an Ir­(III)-catalyzed asymmetric C–H activation enabled by noncovalent interactions. A broad range of sulfur-stereogenic sulfoximines was prepared in high yields with excellent enantioselectivities via the asymmetric C–H activation/annulation of sulfoximines with diazo compounds. Desymmetrization, kinetic resolution, and parallel kinetic resolution are compatible with this protocol. Detailed DFT calculations suggested that the N–H···O hydrogen bonding interaction between sulfoximine and the chiral carboxylic acid ligand was crucial for the high enantiocontrol. Moreover, chiral iridacycle intermediates were isolated, characterized, and subjected to stoichiometric reactions. Computational and experimental studies suggested that the C–H cleavage step was the rate- and enantio-determining step.

Sulfoximines bearing stereogenic sulfur atoms are ubiquitous motifs in pharmaceuticals, agricultural chemicals, and bioactive compounds. Herein, we report the synthesis of sulfur-stereogenic sulfoximines via Co­(III)/chiral carboxylic acid-catalyzed enantioselective C–H amidation. A broad range of cyclic and acyclic sulfur-stereogenic sulfoximines were isolated in good yields and enantioselectivities (up to an 86% yield and 1.5:98.5 er). The acyclic amidation products can be reduced to potential N,S-chiral sulfoxide ligands, which could be further transformed into recyclable chiral auxiliaries in the Pd-catalyzed diastereoselective C­(sp3)–H activation of aliphatic carboxylic acids.

Transition metal-catalyzed enantioselective C−H functionalization has emerged as an efficient and powerful strategy to access various chiral molecules. Recently, this strategy also provided a complementary pathway to the construction of P- and S-stereogenic compounds. In this short review, we summarize the development and applications of various catalytic systems, including Pd(II)/MPAA, Pd(0)/trivalent phosphorus chiral ligand, chiral CpxM(III) (M = Rh, Ir), half-sandwich d6 Ir(III) and Ru(II) with chiral carboxylic acid (CCA) ligand, Ir(I)/chiral bidentate boryl ligand, and Ir(I)/chiral cation, in the access of these chiral compounds via enantioselective C−H functionalization.

P-Stereogenic phosphinamides represent important structural elements in chiral organocatalysts and bioactive compounds. Herein, we report Pd(II)-catalyzed enantioselective C−H alkynylation using cheap commercially available L-pyroglutamic acid as a chiral ligand. A range of structurally diverse P-stereogenic phosphinamides was prepared in good yields with high enantioselectivities via desymmetrization and kinetic resolution. A tailor-made congested directing group, N-ethyl-N-(3methylpyridin-2-yl)amino, was crucial for the reactivity.