Advances in the Chemistry of Oxaziridines

Williamson, Kevin; Michaelis, David J.; Yoon, Tehshik P.

doi:10.1021/cr400611n

Cited by 152 publications

(94 citation statements)

References 214 publications

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“…63 While this cycloaddition is highly indicative of the presence of a nitrone functionality in 7 , oxaziridines are also known to thermally rearrange to nitrones before undergoing 1,3-dipolar cycloadditions. 70,71 …”

Section: Discussionmentioning

confidence: 99%

OxaD: A Versatile Indolic Nitrone Synthase from the Marine-Derived Fungus Penicillium oxalicum F30

et al. 2016

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Indole alkaloids are a diverse class of natural products known for their wide range of biological activities and complex chemical structures. Rarely observed in this class are indolic nitrones, such as avrainvillamide and waikialoid, which possess potent bioactivities. Herein the oxa gene cluster from the marine-derived fungus Penicillium oxalicum F30 is described along with the characterization of OxaD, a flavin-dependent oxidase that generates roquefortine L, a nitrone-bearing intermediate in the biosynthesis of oxaline. Nitrone functionality in roquefortine L was confirmed by spectroscopic methods and 1,3-dipolar cycloaddition with methyl acrylate. OxaD is a versatile biocatalyst that converts an array of semisynthetic roquefortine C derivatives bearing indoline systems to their respective nitrones. This work describes the first implementation of a nitrone synthase as a biocatalyst and establishes a novel platform for late-stage diversification of a range of complex natural products.

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Section: Discussionmentioning

confidence: 99%

OxaD: A Versatile Indolic Nitrone Synthase from the Marine-Derived Fungus Penicillium oxalicum F30

et al. 2016

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“…[36] The table includes as electiono fc atalysts that have been also reported to be active under ambient or very mild reaction conditions:T he bimetallic Al-salen complex reported by North and co-workers ([Al(salen)} 2 O],T able 5, entry 13); [37] aF e III amine triphenolate complex reported by Kleij and co-workers. ([FeTPhOA] 2 ,T able 5, entry 14); [38] ab imetallic Fe III complex reported by Williams and co-workers, [39] bearing at etraimino(amino)diphenol macrocyclic ligand ([LFe 2 Cl 4 ] 2 , Ta ble 5, entry 15) and at etranuclear Zn 4 (OCOCF 3 ) 6 Oc omplex reportedb yM ashima and co-workers(Ta ble5,e ntry 16). [40] Comparison between the TOF values reported in Table 5f or the different catalytic pairs shows that simple Nb and Yh alides compounds are high-performing catalysts for this reaction even when compared to more sophisticated, polymetallic catalytic systems bearing elaborated organic ligands.…”

Section: Cycloadditions Of Co 2 To Epoxidesmentioning

confidence: 93%

“…Good yields were observed in the convenient preparationo fo xazino [4,3-a]indole and 3,4-dihydro-1H-pyrrolo[2,1-c] [1,4]oxazine backbones (6)u nder mild conditions (ranging from ambient temperaturet o8 0 8C). 1H-indol-1-yl-derived oxiranes were candidates for the intramolecular cycloadditionsa nd yieldeds electively the corresponding products (6). Notably,t he CÀO-bondcleavage productsw ere not observed except when using electron-donating groups on the aryl substituents.…”

Section: Cycloadditions To Epoxides With Alkynes Imines and Indolesmentioning

confidence: 99%

“…[1] Dipolar cycloadditions occur specifically between dipolar compounds and dipolarophiles to yield heterocyclic compounds (Scheme 1). Notable examples of scaffolds that can be accessed throught his strategy are triazoles, [2] isoxazoles, [3] pyrrolidines, [4] 6-membered aromatics, [5] isoxazolines, [6] nitrogen heteroaromatics, [7] and [4+ +3] cycloadducts. [8] Epoxidesa re industrially relevant,r eadily availables ubstrates that can be easily accessed from olefins.…”

Section: Introductionmentioning

confidence: 99%

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Cycloadditions to Epoxides Catalyzed by Group III–V Transition‐Metal Complexes

2015

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Complexes of group III–V transition metals are gaining increasing importance as Lewis acid catalysts for the cycloaddition of dipolarophiles to epoxides. This review examines the latest reports, including homogeneous and heterogeneous applications. The pivotal step for the cycloaddition reactions is the ring opening of the epoxide following activation by the Lewis acid. Two modes of cleavage (CC versus CO) have been identified depending primarily on the substitution pattern of the epoxide, with lesser influence observed from the Lewis acid employed. The widely studied cycloaddition of CO2 to epoxides to afford cyclic carbonates (CO bond cleavage) has been scrutinized in terms of catalytic efficiency and reaction mechanism, showing that unsophisticated complexes of group III–V transition metals are excellent molecular catalysts. These metals have been incorporated, as well, in highly performing, recyclable heterogeneous catalysts. Cycloadditions to epoxides with other dipolarophiles (alkynes, imines, indoles) have been conducted with scandium triflate with remarkable performances (CC bond cleavage).

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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.…”

mentioning

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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Advances in the Chemistry of Oxaziridines

Cited by 152 publications

References 214 publications

OxaD: A Versatile Indolic Nitrone Synthase from the Marine-Derived Fungus Penicillium oxalicum F30

OxaD: A Versatile Indolic Nitrone Synthase from the Marine-Derived Fungus Penicillium oxalicum F30

Cycloadditions to Epoxides Catalyzed by Group III–V Transition‐Metal Complexes

Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds

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