A rhodium-catalyzed tandem enantioselective C–H silylation/alkene hydrosilylation of dihydrosilanes, which enables the streamlined construction of a wide range of silicon-stereogenic silanes, is successfully developed. This process involves a SiH2-steered highly enantioselective C–H silylation to furnish the corresponding desymmetric monohydrosilanes, which are subsequently trapped with alkenes in a stereospecific fashion to build functionally diverse asymmetrically tetrasubstituted silanes. This general strategy combines readily available dihydrosilanes and alkenes to construct various enantioenriched silicon-stereogenic silanes, including 9-silafluorenes, Si-bridged ladder compounds, and benzosilolometallocenes, in a single step with good to excellent yields and enantioselectivities.

The exploitation of chirality at silicon in asymmetric catalysis is one of the most intriguing and challenging tasks in synthetic chemistry. In particular, construction of enantioenriched mediem-sized silicon-stereogenic heterocycles is highly attractive, given the increasing demand for the synthesis of novel functional-materials-oriented silicon-bridged compounds. Here, we report a rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarge the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivers various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials.

We disclose a pair of ortho-sulfinylaniline auxiliaries for palladium-catalyzed β–C-H arylation of alkyl carboxamides. Together, these auxiliaries offer a means to effect efficient β-methyl and methylene C–H bond arylation with sterically hindered aryl iodides. ortho-Methylsulfinylaniline (MSOA) enables efficient β-methyl C–H arylation of propanamide substrates with aryl iodides bearing various ortho-substituents including alkyl groups. ortho-Tosylsulfinylaniline (TSOA) enables β-methylene C–H arylation with ortho-substituted aryl iodides. Both amide-linked MSOA and TSOA auxiliaries can be easily removed to give ester products under relatively mild conditions.

An iridium-catalyzed ortho-C(sp)-H amidation reaction of benzaldehydes with organic azides has been developed. A catalytic amount of 3,5-di(trifluoromethyl)aniline was used to promote the Ir-catalyzed directed C-H amination reaction through a transient aldimine intermediate. This reaction tolerates a broad scope of benzaldehyde substrates and works well with a range of aryl- and alkylsulfonyl azides.