Enantioselective Arylation of Sulfenamides to Access Sulfilimines Enabled by Palladium Catalysis

• Published in: Angewandte Chemie 2024-09, Vol.136 (37), p.n/a
• Main Authors: Yuan, Yin, Han, Yidan, Zhang, Zhi‐kun, Sun, Shijin, Wu, Ke, Yang, Junfeng, Zhang, Junliang
• Format: Article
• Language: English
• Subjects: Asymmetric synthesis; Catalysis; Chemical synthesis; Density functional theory; Enantiomers; Functional groups; Insecticides; Ligands; Palladium; Pd Catalysis; Sadphos; Sulfilimines; Sulfur; Sulfur stereogenic centers
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.202409541

Sulfur‐containing functional groups have garnered considerable attention due to their common occurrence in ligands, pharmaceuticals, and insecticides. Nevertheless, enantioselective synthesis of sulfilimines, particularly diaryl sulfilimines remains a challenging and persistent goal. Herein we report a highly enantio‐ and chemoselective cross–coupling of sulfenamides with aryl diazonium salt to construct diverse S(IV) stereocenters by Pd catalysis. Bisphosphine ligands bearing sulfinamide groups play a crucial role in achieving high reactivity and selectivity. This approach provides a general, modular and divergent framework for quickly synthesizing chiral sulfilimines and sulfoximines that are otherwise challenging to access. In addition, the origins of the high chemoselectivity and enantioselectivity were extensively investigated using density functional theory calculations. The highly enantio‐ and chemoselective cross–coupling of sulfenamides with aryl diazonium salt to construct diverse S(IV) stereocenters was developed. This strategy offers a general, modular and divergent platform for rapid synthesis of chiral sulfilimines and sulfoximines that are otherwise difficult to access.