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Planar chiral [2.2]paracyclophanes, particularly pseudo‐disubstituted derivatives, are privileged scaffolds for chiral ligands and catalysts in asymmetric synthesis and have widespread applications in materials science. However, catalytic asymmetric approaches for the enantioselective synthesis of pseudo‐disubstituted [2.2]paracyclophanes remain underexplored. In this study, we introduce a novel class of peptide‐iminophosphorane organosuperbases to induce planar chirality in spatially stacked [2.2]paracyclophanes. This efficient protocol enables the enantioselective synthesis of a diverse array of structurally distinct pseudo‐gem, pseudo‐ortho, and pseudo‐para [2.2]paracyclophanes, achieving high yields and excellent enantioselectivities via desymmetrization or kinetic resolution. Moreover, the products can be readily diversified through various functional group transformations. Mechanistic investigations provide valuable insights into the unique stereocontrol exhibited by this peptide‐iminophosphorane catalytic system.

In this study, we have discovered the versatility of the dithiosulfonate reagent (ArSO2‐SSR) in transition metal catalyzed selective hydrodisulfuration of unactivated alkenes. The hydrodisulfuration displays a unique Markovnikov selectivity with a Salen‐cobalt complex, while an anti‐Markovnikov selectivity is observed when employing a nickel/bidentate N‐donor ligand. Furthermore, precise control over nickel/ligand enables the successful achievement of remote site‐selective hydrodisulfuration for both internal and terminal alkenes via a chain‐walking process. In these processes, silanes are employed as a hydride source. Mechanistic insights into these innovative catalytic systems are also elucidated. Experimental findings suggest that Markovnikov hydrodisulfuration is likely to proceed through radical substitution on dithiosulfonate reagents, while nickel catalyzed anti‐Markovnikov selectivity and remote site‐selectivity likely occur via the radical addition of the reductively formed dithiosulfonate radical anion ([ArSO2‐SSR]⋅−) to alkyl Ni(II) species (alkyl‐Ni(II)LnX) and subsequent reductive elimination on Ni(III) intermediate (alkyl–Ni(III)Ln(X)‐SSR) as the key steps based on DFT calculation analysis.