Catalytic asymmetric synthesis of [2,3]-fused indoline heterocycles through inverse-electron-demand aza-Diels-Alder reaction of indoles with azoalkenes.

An unprecedented catalytic asymmetric inverse-electron-demand aza-Diels-Alder reaction of indoles with in situ formed azoalkenes is reported. A diverse set of [2,3]-fused indoline heterocycles were achieved in generally good yields (up to 97 %) with high regioselectivity and diastereoselectivity (>20:1 d.r.), and with excellent enantioselectivity (up to 99 % ee).

Catalytic asymmetric 1,3-dipolar cycloaddition of two different ylides: facile access to chiral 1,2,4-triazinane frameworks.

Ylides at a crossing: An unprecedented 1,3-dipolar cycloaddition (cross-cycloaddition) between two different ylides was realized by using the chiral Cu(I) /tBu-Phosferrox complex as the catalyst under mild reaction conditions. This catalytic system provides an expeditious approach to the construction of highly functionalized 1,2,4-triazinane derivatives in good yields with excellent diastereoselectivities and enantioselectivities.

Asymmetric construction of trifluoromethylated pyrrolidines via Cu(I)-catalyzed 1,3-dipolar cycloaddition of azomethine ylides with 4,4,4-trifluorocrotonates.

Trifluoromethylated pyrrolidines have been synthesized via catalytic asymmetric 1,3-dipolar cycloaddition with excellent stereoselectivity for the first time. Epimerization of the endo-pyrrolidines obtained from cis-4,4,4-trifluorocrotonate into the exo-pyrrolidines was also revealed.

Organocatalytic asymmetric Michael addition of alpha-aryl cyclopentanones to nitroolefins for construction of adjacent quaternary and tertiary stereocenters.

The first asymmetric Michael addition of alpha-aryl cyclopentanones to nitroolefins for construction of adjacent quaternary and tertiary stereocenters has been achieved with excellent diastereo-/enantioselectivity.