Advances in Stereoselective Iron(II)‐Catalyzed Synthesis of Sulfilimines with <i>N</i>‐Mesyloxycarbamates

Lebel, H.; Lai, Calvine

doi:10.1002/hlca.202100209

Cited by 2 publications

(1 citation statement)

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“…Further stereospecific oxidation of chiral sulfimides enables access to enantioenriched sulfoximines, which have garnered increasing recognition in medicinal chemistry and agricultural science. , Among various methods documented in the literatures, ,, transition-metal-catalyzed enantioselective nitrenoid transfer to sulfides is a highly efficient strategy for rapid construction of sulfimides in the enantioenriched form (Scheme b). Inspired by the original studies of Kwart and Khan, metal nitrenoids have been employed as versatile intermediates in numerous nitrene transfer reactions encompassing insertion into heteroatom lone pairs, addition to alkenes, insertion into C–H bonds, and so on. − Remarkable progress has been achieved in the realm of the asymmetric imidation of sulfides. Uemura and Taylor reported early examples with chiral copper(I)/bis(oxazoline) , as the catalyst, affording moderate enantioselectivities.…”

Section: Introductionmentioning

confidence: 99%

Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer

Liu,

Wu,

Zhang

et al. 2024

J. Am. Chem. Soc.

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Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction of enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose a chiral iron(II)/N,N′-dioxide-catalyzed enantioselective imidation of dialkyl and alkyl aryl sulfides using iminoiodinanes as nitrene precursors. A series of chiral sulfimides were obtained in moderate-to-good yields with high enantioselectivities (56 examples, up to 99% yield, 98:2 e.r.). The utility of this methodology was demonstrated by late-stage modification of complex molecules and synthesis of the chiral insecticide sulfoxaflor and the intermediates of related bioactive compounds. Based on experimental studies and theoretical calculations, a water-bonded high-spin iron nitrenoid species was identified as the key intermediate. The observed stereoselectivity was original from the steric repulsion between the amide unit of the ligand in the chiral cave and the bulky substituent of sulfides. Additionally, dioxazolones proved to be suitable acylnitrene precursors in the presence of an iron(III)/N,N′dioxide complex, resulting in the formation of enantioselectivity-reversed sulfimides (14 examples, up to 81% yield, 97:3 e.r.).

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