Terpyridine-type ligands were renowned for their rich coordination with various metal ions. However, their high cost and tedious preparation methods limit their further application in asymmetric catalysis. Herein, we prepared diverse crab-shape C2-symmetric chiral terpyridine-tethered bisulidine ligands (abbreviated as Tpy-bisulidines), readily derived from optically pure sulfonylated 1,2-diphenylethylenediamine, in operationally simple one step and up to 57% yield. They were proven to be a class of efficient chiral ligands for Ni(II)-catalyzed asymmetric inverse-electron-demand Hetero-Diels-Alder reactions (HDA) between β,γ-unsaturated α-ketoesters and electron-rich alkenes, such as 2,3-dihydrofuran and enecarbamates, affording the products in excellent enantioselectivities. In addition to the HDA reaction, the in-situ-generated chiral Tpy-bisulidines/Ni(OTf)2 complex was also applied in the asymmetric Michael addition, Friedel-Crafts alkylation and Mukaiyama-Michael reactions, achieving high stereoselectivities. These findings demonstrate the promising potential of the Tpy-bisulidine ligand as a privileged ligand for diversity-oriented asymmetric catalysis.

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