The Baldwin Rearrangement: Synthesis of 2‐Acylaziridines

Tangara, Salia; Kanazawa, Alice; Py, Sandrine

doi:10.1002/ejoc.201700920

Cited by 23 publications

(17 citation statements)

References 100 publications

(68 reference statements)

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“…Subsequent reductive eliminationo fP hI yields iminoisoxazoline C or isothiazoline 4a. Due to the instability of the NÀObond under the reactionconditions, intermediate C undergoes further Baldwin rearrangement [23] to afford oxazoline 2a through olefinic C=Cb ond cleavage/cyclization of the iminoacyl-aziridine species D.T he formation of isothiazoline has suggested that the NÀSb ond in 4a is stable under the stated conditions, whereas the NÀO bond in isoxazoline C cannotwithstand the reactionconditions and thus undergoes further NÀOc leavager eaction to form oxazoline 2a.…”

mentioning

confidence: 99%

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

Guo

Huang

Jiang

et al. 2018

Chemistry A European J

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The hypervalent iodine reagent PhI(OAc) (PIDA) mediated the formal oxidative C=C bond cleavage and subsequent cyclization of internal olefins, that is, α-oxo-ketene N,N-acetals, which afforded substituted oxazolines. Isothiazoline derivatives were obtained from the reactions of α-thioxo-ketene N,N-acetals with PIDA under the same conditions. Hydrolysis of the resultant oxazoline derivatives led to highly functionalized oxazolones. A plausible mechanism was proposed based upon the formation of isothiazoline-type intermediates.

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mentioning

confidence: 99%

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

Guo

Huang

Jiang

et al. 2018

Chemistry A European J

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“…The initial strategy was revised; functional group manipulations of 1.7 furnished nitrone 1.8 , which was primed for a [3+2] cycloaddition. Heating 1.8 in toluene gave aziridine 1.10 , presumably obtained via an unexpected Baldwin rearrangement of 1.9 [9c] . Nishikawa surmised 1.10 might be useful if the correct C3 stereochemistry was present, though the origins of the stereoselectivity were not remarked upon.…”

Section: Syntheses Of the Core Of Pactamycinmentioning

confidence: 99%

Strategies for the Syntheses of Pactamycin and Jogyamycin

2021

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Pactamycin and jogyamycin are aminocyclopentitol natural products, where each core carbon bears a stereodefined alcohol or amine moiety. Their structural complexity, coupled with the diversity of functional groups coexisting in a condensed space, make them fascinating synthetic targets in their own right. Pactamycin and its derivatives bind to the 30S ribosomal subunit and display activity against parasites responsible for drug‐resistant malaria and African sleeping sickness; however, efforts to develop their therapeutic potential have been hampered by their cellular toxicity. Interestingly, bioengineered analogues display differences in selectivity and toxicity towards mammalian cells, spurring efforts to develop flexible strategies to thoroughly probe structure–activity relationships (SAR), particularly in analogues lacking the C7 hydroxyl group of pactamycin. This review compares and contrasts approaches towards pactamycin and jogyamycin, including two successful total syntheses of the former. The implications of each route for preparing analogues to inform SAR and lead to compounds with increased selectivity for binding malarial over human ribosomes are briefly discussed.

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“…Die Anfangsstrategie wurde dahingehend überarbeitet, dass durch Modifikationen funktioneller Gruppen von 1.7 das Nitron 1.8 erzeugt wurde, das für eine [3+2]‐Cycloaddition geeignet war. Durch Erhitzen von 1.8 in Toluol wurde das Aziridin 1.10 erhalten, das vermutlich über eine unerwartete Baldwin‐Umlagerung von 1.9 entstand [9c] . Nishikawa vermutete, dass 1.10 verwendet werden könnte, falls die richtige C3‐Konfiguration vorlag, wenngleich nichts über die Stereoselektivität angemerkt wurde.…”

Section: Synthesen Des Kerns Von Pactamycinunclassified

Strategien für die Synthese von Pactamycin und Jogyamycin

2021

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Pactamycin und Jogyamycin sind Aminocyclopentitol‐Naturstoffe, deren Kohlenstoffkern stereochemisch definierte Alkohol‐ oder Amineinheiten trägt. Aufgrund ihrer strukturellen Komplexität sowie der Vielfältigkeit der funktionellen Gruppen auf engem Raum sind sie faszinierende Syntheseziele. Pactamycin und dessen Derivate binden zur ribosomalen 30S‐Untereinheit und zeigen Wirkung gegen Parasiten, die arzneimittelresistente Malaria und afrikanische Schlafkrankheit verursachen; jedoch wird die Weiterentwicklung ihres therapeutischen Potenzials durch zelluläre Toxizität gebremst. Interessanterweise zeigen biotechnologisch erzeugte Analoga Unterschiede in der Selektivität und Toxizität in Säugerzellen, was die Entwicklung flexibler Strategien zur genauen Untersuchung der Struktur‐Wirkungs‐Beziehungen (SARs), insbesondere von Pactamycinanaloga ohne C7‐Hydroxygruppe, anspornt. In diesem Aufsatz werden Ansätze zur Synthese von Pactamycin und Jogyamycin gegenübergestellt, einschließlich zweier Totalsynthesen von Pactamycin. Wir diskutieren kurz die Bedeutung jeder Syntheseroute zu Analoga für die Untersuchung von SARs und die Entwicklung von Verbindungen mit erhöhter Selektivität für die Bindung an Ribosomen des Malariaerregers anstelle menschlicher Ribosomen.

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The Baldwin Rearrangement: Synthesis of 2‐Acylaziridines

Abstract: International audienc

Cited by 23 publications

References 100 publications

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

Strategies for the Syntheses of Pactamycin and Jogyamycin

Strategien für die Synthese von Pactamycin und Jogyamycin

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