Synthesis of О-2-(acyl)vinylketoximes and their unusual rearrangements into 2- and 3-acyl-substituted pyrroles

Glotova, T. E.; Schmidt, Elena Yu.; Dvorko, Marina Yu.; Ushakov, Igor А.; Михалева, А. И.; Трофимов, Б. А.

doi:10.1016/j.tetlet.2010.09.101

Cited by 10 publications

(2 citation statements)

References 24 publications

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“…Subjection of O -2-acylvinyloximes 10 to the standard gold(I)-catalyzed rearrangement conditions afforded the desired pyrroles 11 / 12 in moderate to good yield. Because of competing cyclization modes, ketone derivatives 10b and 10c gave a mixture of pyrroles 11 / 12 …”

Section: Resultsmentioning

confidence: 99%

Development of a Gold-Multifaceted Catalysis Approach to the Synthesis of Highly Substituted Pyrroles: Mechanistic Insights via Huisgen Cycloaddition Studies

2013

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A novel gold-catalyzed method for the regioselective synthesis of highly substituted pyrroles directly from oximes and alkynes was developed via independent optimization of two key steps of the process. Importantly, a cationic gold(I) species was shown to activate multiple steps along the reaction pathway and therefore act as a multifaceted catalyst. Initial gold-promoted addition of the oxime oxygen to the activated alkyne afforded the O-vinyloxime in situ. The O-vinyloxime was subsequently transformed into the pyrrole via a gold-catalyzed tautomerization, [3,3]-sigmatropic rearrangement, and cyclodehydration process. Notably, this method provides a functional group handle in the form of an ester at the 3/4-position for further exploitation. The proposed mechanistic pathway is supported by a novel application of the Huisgen cycloaddition click reaction, which was used to probe the relative stability of substituted O-vinyloximes. The intermediacy of N-alkenylhydroxylamine O-vinyl ethers and imino ketones or imino aldehydes along the reaction pathway were determined by high-temperature (1)H, (2)H{(1)H}, and (13)C{(1)H} NMR experiments. X-ray crystallographic evidence was used to further support the mechanistic hypothesis.

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Section: Resultsmentioning

confidence: 99%

Development of a Gold-Multifaceted Catalysis Approach to the Synthesis of Highly Substituted Pyrroles: Mechanistic Insights via Huisgen Cycloaddition Studies

2013

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“…A metal-free route for O -vinylation of oximes includes the nucleophilic addition of oximate species to the alkyne CC bond in superbasic media (for recent works, see refs − ) or to electrophilically activated allenes in the presence of a base (for recent works, see refs and ). In the presence of a metal center, the set of reagents is extended to vinyl boronic acids; furthermore, metal-involving protocols allow the reactions with alkynes to proceed under significantly milder conditions than in metal-free methods.…”

Section: Metal-mediated Reactions Of the Oxime Groupmentioning

confidence: 99%

Metal-Involving Synthesis and Reactions of Oximes

et al. 2017

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This review classifies and summarizes the past 10-15 years of advancements in the field of metal-involving (i.e., metal-mediated and metal-catalyzed) reactions of oximes. These reactions are diverse in nature and have been employed for syntheses of oxime-based metal complexes and cage-compounds, oxime functionalizations, and the preparation of new classes of organic species, in particular, a wide variety of heterocyclic systems spanning small 3-membered ring systems to macroheterocycles. This consideration gives a general outlook of reaction routes, mechanisms, and driving forces and underlines the potential of metal-involving conversions of oxime species for application in various fields of chemistry and draws attention to the emerging putative targets.

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ChemInform Abstract: Synthesis of O‐2‐(Acyl)vinylketoximes (III) and Their Unusual Rearrangements into 2‐ and 3‐Acyl‐substituted Pyrroles.

et al. 2011

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Synthesis of О-2-(acyl)vinylketoximes and their unusual rearrangements into 2- and 3-acyl-substituted pyrroles

Cited by 10 publications

References 24 publications

Development of a Gold-Multifaceted Catalysis Approach to the Synthesis of Highly Substituted Pyrroles: Mechanistic Insights via Huisgen Cycloaddition Studies

Development of a Gold-Multifaceted Catalysis Approach to the Synthesis of Highly Substituted Pyrroles: Mechanistic Insights via Huisgen Cycloaddition Studies

Metal-Involving Synthesis and Reactions of Oximes

ChemInform Abstract: Synthesis of O‐2‐(Acyl)vinylketoximes (III) and Their Unusual Rearrangements into 2‐ and 3‐Acyl‐substituted Pyrroles.

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