2019
DOI: 10.1021/acs.joc.9b01023
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Organocatalytic Olefin Aziridination via Iminium-Catalyzed Nitrene Transfer: Scope, Limitations, and Mechanistic Insight

Abstract: Olefin aziridination via organocatalytic nitrene transfer offers potential complementarity to metalcatalyzed methods, however there is a lack of reports of such reactions in the literature. Herein is reported a method that employs an iminium salt to catalyze the aziridination of styrenes by [N-(ptoluenesulfonyl)imino]phenyliodinane (PhINTs). These reactions are hypothesized to proceed via a diaziridinium salt as the active oxidant. In addition to outlining the scope and limitations of the method, evidence for … Show more

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Cited by 21 publications
(10 citation statements)
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“…The transition-metal catalyzed aziridination of alkene with nitrene precursors is the most popular and commonly used approach to construct an aziridine subunit 26 , 28 , 34 . Recently, metal-free and catalyst-free aziridination of alkenes have emerged as greener alternatives, but only limited approaches are available 62 – 65 . Among them, photo-induced aziridination of alkenes with iminoiodinanes seems to be a promising tool, but high energy ultraviolet (UV)-irradiation was used in this protocol 64 .…”
Section: Introductionmentioning
confidence: 99%
“…The transition-metal catalyzed aziridination of alkene with nitrene precursors is the most popular and commonly used approach to construct an aziridine subunit 26 , 28 , 34 . Recently, metal-free and catalyst-free aziridination of alkenes have emerged as greener alternatives, but only limited approaches are available 62 – 65 . Among them, photo-induced aziridination of alkenes with iminoiodinanes seems to be a promising tool, but high energy ultraviolet (UV)-irradiation was used in this protocol 64 .…”
Section: Introductionmentioning
confidence: 99%
“…Regarding existing aziridination methods (Scheme a), a large body of work has used hypervalent iodine compounds such as N -tosyliminophenyliodinane (PhINTs) and derivatives , but also phthalimides, , sulfonamides, , chloramine-T, N -sulfonyl imines, azides like 2,2,2-trichloroethoxysulfonyl azide (TcesN 3 ), , and others, with frequent use of homogeneous transition metal catalysts. Although these methods can produce aziridines even from unactivated alkenes in some cases, they all form N -protected aziridines.…”
Section: Introductionmentioning
confidence: 99%
“…The discovery of different modes of catalytic nitrene transfer that are distinct from existing transition metal-catalyzed methods holds promise for hastening the development of reactions exhibiting complementary selectivity . Recently, the Hilinski laboratory disclosed the first example of organocatalytic nitrene transfer and demonstrated the method’s capability in the context of site-selective C­(sp 3 )–H amination (Scheme ) and aziridination . The catalyst, an iminium salt, is proposed to react with an iminoiodinane nitrene precursor to produce a diaziridinium salt as the active oxidant, which then reacts with the substrate to produce the observed product and regenerate the catalyst (Scheme ).…”
Section: Introductionmentioning
confidence: 99%
“…6 Recently, the Hilinski laboratory disclosed the first example of organocatalytic nitrene transfer and demonstrated the method's capability in the context of site-selective C(sp 3 )−H amination 7 (Scheme 1) and aziridination. 8 The catalyst, an iminium salt, is proposed to react with an iminoiodinane nitrene precursor to produce a diaziridinium salt 9 as the active oxidant, which then reacts with the substrate to produce the observed product and regenerate the catalyst (Scheme 1). Conceptually, this extends organocatalytic atom-transfer oxidation reactions, which are well established for oxygen transfer via dioxirane and oxaziridinium intermediates, to nitrene transfer.…”
Section: Introductionmentioning
confidence: 99%