Oxaziridines and Oxazirines

Davis, Franklin A.; Chen, B.-C.; Zhou, Peng

doi:10.1016/b978-008044992-0.00112-7

Cited by 8 publications

(6 citation statements)

References 215 publications

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“…When arylzinc halide 1 was reacted with three different oxaziridines ( 3 – 5 ), formation of the desired aniline 2 was not observed (Table entry 1). These results indicated that the balance of arylmetal basicity and nucleophilicity does not fall in the optimal range required for the amination by an NH oxaziridine . The aggregation of organozinc molecules in solution likely renders them insufficiently nucleophilic for a successful direct amination, in contrast to the observed behavior of aryl Grignard reagents …”

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confidence: 99%

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Zhou

Behnke

et al. 2016

J. Am. Chem. Soc.

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Herein we disclose a novel method for the facile transfer of primary (–NH2) and secondary amino groups (–NHR) to heteroaryl- as well as arylcuprates at low temperature without the need for precious metal catalysts, ligands, excess reagents, protecting and/or directing groups. This one-pot transformation allows unprecedented functional group tolerance and it is well-suited for the amination of electron-rich, electron-deficient as well as structurally complex (hetero)arylmetals. In some of the cases, only catalytic amounts of a copper(I) salt is required.

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confidence: 99%

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

Zhou

Behnke

et al. 2016

J. Am. Chem. Soc.

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“…Compared with the widely used and studied N -sulfonyloxaziridines (for example, Davis’ oxaziridines), N–H oxaziridines have been exploited only rarely in synthesis because of their perceived low stability/high reactivity. However, a handful of bench-stable N–H oxaziridines have been reported and used for the amination of alcohols and enolates, albeit in fairly limited ways 39,40,42,43 . N–H oxaziridines (Fig.…”

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confidence: 99%

Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds

et al. 2016

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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C–C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (–NH2) and hydroxyl (–OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N–H and N–alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts/ligands/additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.

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“…On heating, it is known that nitrones rearrange to oxaziridines, and oxaziridines rearrange to amides. 14 However, heating oxaziridine 13 under the reaction conditions resulted in no reaction. When 13 was heated at 110 °C for 96 h in the presence of a catalytic amount of peroxorhenium complex amide (S)-(+)-12 was obtained in 51% yield.…”

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confidence: 99%

“…With the dehydropyrrolidines (+)- 9 in hand the idea was to oxidize them to the corresponding nitrones with the expectation that on heating they would undergo an intramolecular [3 + 2] cycloaddition to give tricyclic isoxazolidines. While most oxidations of imines lead to oxaziridines, Goti and co-workers recently described the catalytic oxidation of imines to nitrones with urea hydrogen peroxide (UHP) catalyzed by methyltrioxorhenium (MTO) . Oxidation of (+)- 9 with 3.3 equiv of UHP and cat.…”

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confidence: 99%