Optically active cis-cyclopropane carboxylates are prepared via the Rh2(S-PTAD)4-catalyzed cyclopropanation of α-silyl styrenes with aryl diazoacetates followed by desilylation of the resulting silyl cyclopropane carboxylates. The conjugation of the aryl ring with C═C bond and π stacking are proposed for the stereoselectivity of cyclopropanation, and configuration inversion is observed with the desilylation process.

The chiral Cu-complex-catalyzed intramolecular interception of meso-α,α′-diazido alcohols with aryldiazoacetates is explored. Most of the enantioenriched α-imino esters with three continuous stereocenters are produced with good to excellent yield and enantioselectivity, and a chiral pocket model is proposed for rationalization of the asymmetric desymmetrization.

The preparation of substituted pyrrolizines through the Schmidt reaction of acyl chlorides with alkyl azides has been realized. Intramolecular capture of the isocyanate ion and N-acyliminium ion intermediates from the Schmidt process with alkene or alkyne units was achieved, and the efficiency of the conversion with respect to ring construction and bond formation was demonstrated.

A catalytic diastereo- and enantiocontrolled preparation of cis-β-fluorocyclopropane carboxylates through the Rh-catalyzed cyclopropanation of alkenyl fluorides with diazoarylacetates has been realized. Rh2(S-DOSP)4 and benzyl diazoarylacetates were found to be beneficial to the cyclopropanation with high diastereoselectivity. Thirteen cis-β-fluorocyclopropane carboxylates were prepared in hexane at 0 °C with good to excellent yields. The enantiomeric excess was up to 97%, and the diastereomer ratio was up to 95:5.

Intramolecular Schmidt reaction of acyl chlorides with alkyl azides through N-acyliminium ion intermediates is designed and realized. The intramolecular capture of the intermediates with aromatic rings affords several nitrogen-containing tricyclic skeletons. The important feature of the domino process is the efficiency in bond reorganization and ring formation.

The first catalytic enantioselective desymmetrization of 1,3-diazido-2-propanol via an intramolecular interception of alkyl azides by Cu–carbenoids has been realized. A wide range of 1,3-diazidoisopropyl diazo(aryl)acetates were converted to cyclic α-imino esters in the presence of bisoxazoline ligand (S,S)-Ph-Box with good to excellent yields, and the enantiomeric excess was up to 97%.

The asymmetric transfer hydrogenation of racemic β-azidocyclopropane carboxylates has been explored. Ru-TsDPEN B is found to be a good catalyst for the formation of enantioenriched γ-lactones through a four-step sequence of azide reduction/cyclopropane ring cleavage/ketone transfer hydrogenation/lactonization, and the enantiomeric excess of the lactones was up to 94%.

An efficient preparation of (±)-antofine is described. The main steps involved in this synthesis are the Horner–Wadsworth–Emmons reaction, the intramolecular Schmidt reaction of an azido aldehyde, and the one-pot deprotection of the N-formyl group, followed by Pictet–Spengler cyclization. The asymmetric hydrogenation of the trisubstituted α,β-unsaturated ester is also explored, however only moderate enantio-control (55% ee) is obtained. Finally, (±)-antofine is prepared in six steps from the phenanthryl aldehyde 5 with an overall yield of 35%.

A formal metal-free N-arylation of aromatic aldehydes with 3-azido-N-tosylpropan-1-amine through the Schmidt process was realized in the presence of acids. TfOH was found to be a good promoter, and the exclusive 1,2-aryl migration was observed. Furthermore, the conversion of an aliphatic aldehyde to the N,N-disubstituted formamide was achieved in excellent yield.

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.

The first intramolecular Schmidt reaction of acyl chlorides with alkyl azides has been developed. In this one-pot conversion, an ω-azido hydrocinnamic acid is converted to a tricyclic lactam. The most important feature of the process is the efficiency in bond formation (one bond broken and three new bonds created) and ring construction (two new rings formed).

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.

The preparation of substituted pyrrolizines through the Schmidt reaction of acyl chlorides with alkyl azides has been realized. Intramolecular capture of the isocyanate ion and N-acyliminium ion intermediates from the Schmidt process with alkene or alkyne units was achieved, and the efficiency of the conversion with respect to ring construction and bond formation was demonstrated.