转自：康龙化成

Iron-catalysed Stereoselective NH Transfer Enables 

Dynamic KineticResolution of Sulfoxides

Fang-XuFan1, Hui Xu2,,Shi-Xiong Tang1, Yanfeng Dang2 & Fei Wang1

StateKey Laboratory of Elemento-OrganicChemistry, Frontiers Science Center for New Organic Matter, College ofChemistry, Nankai University,Tianjin 300071, China.

TianjinKey Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry,Tianjin University, Tianjin 300072, China

—Nature Communication, 2025, DOI: 10.1038/s41467-025-56860-4

Recommended by Yuquan Liu_PT

KEYWORDS:Fecatalysis, photo chemistry, dynamic kinetic resolution (DKR), asymmetric synthesis (反应类型), S=N(成键类型), sulfoxides (原料), sulfoximines (产物), PivO-NH3OTf, O-pivaloyl hydroxyl ammonium trifluoromethane sulfonate (其他)

ABSTRACT: Transitionmetal-catalysed asymmetric nitrene transfer provides a powerful means to access variousbioactive N-containing compounds as single enantiomers. However,enantioselective NH transfer that allows concise assembly of unprotectedenantioenriched amines remains an enduring challenge. We report here an iron-catalysed stereoselective NH imidation ofsulfoxide, which is integrated with photocatalytic racemisation ofsulfoxide, enabling a dynamic kinetic resolution (DKR) strategy for direct andasymmetric synthesis of NH-sulfoximines.This approach is distinct from the existing methods by avoiding protectinggroup manipulations and/or the use of chiral substrates. Computational studieson the NH imidation reaction suggest the involvement of an iron-aminyl radical intermediate, and its reactionwith sulfoxide proceeds through a synchronous nucleophilic addition ofsulfoxide to nitrogen center and ligand-to-metal single electron transferprocess to form the N–S bond. In addition, the stereoselectivity is primarilydictated by the difference in dispersion interactions of the transition states.

Transitionmetal-catalysed nitrene transfer and dynamic kinetic resolution approach for asymmetric synthesis of NH-sulfoximines

Substrate scope (selected)

Further conversions of 2

The proposed reaction pathway

Prof.Fei Wang et alhave reported a relay catalysis-enabled DKR ofsulfoxide for asymmetric NH-sulfoximine synthesis that include an iron-catalysed stereoselective NH transfer to sulfoxide with iQuinox ligand and photoredox catalysis for racemisation of chiral sulfoxide.The reaction provides a new catalysis paradigm for direct synthesis of chiralNH-sulfoximines,avoiding protecting group manipulations and/or the use of chiral substrates.Mechanistic studies suggested the intermediacy of an iron-aminylradical, and the N–S bond is formed via a synchronous nucleophilic addition ofsulfoxide to nitrogen centerand ligand-to-metal single electron transfer process. The results also indicatethe feasibility of stereoselective NH transfer using earth-abundant ironcatalyst, setting the stage for the development of other asymmetric NH transferreactions. The success in merging photocatalytic racemisation ofchiral sulfoxides and its catalytic stereoselective conversion should also haveimportant impacts on the discovery of other DKR transformations of sulfoxides.

（转自：康龙化成）