Catalyst-controlled divergent intermolecular cycloadditions of vinylaziridines with alkynes have been developed. By using [Rh(NBD)2]BF4 as the catalyst, a [3 + 2] cycloaddition reaction was achieved with broad substrate scope and high stereoselectivity under mild reaction conditions. Moreover, the chirality of vinylaziridines can be completely transferred to the [3 + 2] cycloadducts. When the catalyst was changed to [Rh(η(6)-C10H8) (COD)]SbF6, the alternative [5 + 2] cycloadducts were selectively formed under otherwise identical conditions.

A novel type of highly efficient chiral sulfinamide bisphosphine catalysts (Wei-Phos) were developed. These could be easily prepared from commercially available starting materials. Wei-Phos has shown good performance in the very challenging intermolecular cross-Rauhut-Currier reactions of vinyl ketones and 3-acyl acrylates or 2-ene-1,4-diones, leading to the R-C products in high yields with up to 99% ee under 2.5-5 mol% catalyst loading. The highly regio- and enantio-selective cross-Rauhut-Currier reactions of 2-ene-1,4-diones and vinyl ketone have yet reported so far.

A new synthetic application of vinyl aziridines as N-containing three-atom components in a rhodium-catalyzed [4+3] cycloaddition reaction is described. The reaction proceeds well with various silyl dienol ethers and vinyl aziridines, and enables the efficient synthesis of highly functionalized azepines in an enantioselective manner with net inversion of absolute configuration. The salient features of the transformation include the use of readily available substrates, high selectivity, and mild reaction conditions, as well as the versatile functionalization of the products.

Herein we present a phoshine-catalyzed highly regio-, diastereo- and enantioselective [3 + 2] cycloaddition of γ-substituted allenoates with β-perfluoroalkyl enones, delivering a wide range of densely functionalized perfluoroalkylated cyclopentenes with three contiguous chiral stereocenters.

An atom-economic route to ring-fused 1,2,4-hexahydrotriazines relying upon a new synthetic application of vinylaziridines in a rhodium-catalyzed intermolecular [3+3] cycloaddition of C,N-cyclic azomethine imines has been reported. Highly efficient chirality transfer in the present transformation was also observed, providing a new method for the synthesis of sp-carbon-rich 1,2,4-hexahydrotriazines in an enantioselective manner.