•Asymmetric hydrogenation of 1-silyl-1-substituted alkenes is addressed.•Chiral silanes are produced with good to excellent enantioselectivity.•Cationic N,P-Ir complexes are employed.•Polar solvent contributes to the excellent enantioselectivity.Asymmetric hydrogenation of 1-silyl-1-substituted alkenes has been explored, producing eight optically active silanes with good to excellent enantioselectivity (66–99% ee) and yield (74–99%). The reaction was efficiently catalyzed by the cationic N,P-Ir complexes, and the polar solvents were found to be essential for the stereocontrol of the conversion.

•The first intermolecular Schmidt reaction of acyl silanes is addressed.•The Schmidt reaction proceeds with absolute site selectivity.•The amides are produced with good to excellent yield.•The silyl group accelerates the rearrangement process.The first intermolecular Schmidt reaction of alkyl azides with acyl silanes has been designed and realized, producing a range of amides with absolute site selectivity in good to excellent yields. The mechanism of the conversion has been proposed, and the reaction exhibits scope of substrates.

The asymmetric transfer hydrogenation of α-azido acrylates has been explored, a range of α-hydroxy esters are produced with good enantioselectivities (80–90% ee). The reaction was conducted in the wet HCO2H/NEt3 with Ru-TsDPEN A.

An efficient preparation of imidazolines from nitriles and aziridines in the presence of TfOH via Ritter reaction is described. It indicates that different kinds of nitriles can undergo the process. Among the nitriles, pivalonitrile is proven to be better than acetonitrile. The reaction is performed at room temperature and the yields are excellent.An efficient TfOH-promoted Ritter reaction of nitriles with aziridines to imidazolines is described.

An efficient and practiced procedure for the preparation of γ-oxo esters from the β-azidocyclopropane esters has been developed. Ph3P was proven to be a good promoter in THF/H2O, and 11 γ-oxo esters were prepared in 73–99% yields under mild and neutral conditions.

A diastereo- and enantiocontrolled preparation of the conformationally restricted cis-β-azidocyclopropane esters have been developed. The Rh2(S-DOSP)4 was found to be an efficient catalyst in hexane for the cyclopropanation of azido alkenes with diazo esters, and 19 cis-β-azidocyclopropane esters were prepared in excellent yields. The value of the diastereomer ratio was up to 99:1, and the enantiomeric excess was up to 95%. Furthermore, the relative and absolute configuration was confirmed by X-ray analysis.