Triphenylphosphine as an effective catalyst for ketoximes addition to acylacetylenes: regio- and stereospecific synthesis of (E)-(O)-2-(acyl)vinylketoximes

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

doi:10.1016/j.tet.2010.07.057

Cited by 20 publications

(6 citation statements)

References 30 publications

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“…yield in 2 stages. The spectroscopic data of synthetic (-)mesembrane ( 53) and (+)-crinane (55) are identical to the data for natural products.…”

Section: Review Synthesissupporting

confidence: 59%

“…To provide greater substitution around the pyrrole ring, the synthesis of pyrroles from the oximes and the aryl-substituted alkynes was investigated. 54 When using the modified Trofimov procedure, 55 an ester and keto-substituted O -vinyloximes 90 were obtained as a result of the addition of the ketoxime 79c to the acylacetylenes 80 catalyzed by triphenylphosphine. Introduction of O -2-acylvinyloximes 90 under the standard gold(I)-catalyzed rearrangement conditions allowed to obtain the desired 91 / 92 in moderate yield.…”

Section: Intermolecular Reactions Leading To Tetrahydroindolesmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances in the Synthesis of Indoles with Partially Hydrogenated Benzene Ring (Tetrahydroindoles)

Mamedov,

Zhukova

2023

Synthesis

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In this review, a fragmentary analysis of 4,5,6,7-tetrahydroindoles was performed and, on its basis, the existing methods of their synthesis published over the past 15 years have been summarized, and analyzed, as well as, if necessary, an analysis of earlier works is carried out. The proposed reaction mechanism is considered, as well as factors that significantly influence the course of the process. Among such factors: temperature, type and content of the catalyst, promoting additives, method of the process, etc. Particular attention is paid to fundamentally new methods that make it possible to synthesize various derivatives of the mentioned heterocyclic systems from available and cheap reagents, and in some cases under environmentally benign conditions.1 Introduction2 Intramolecular Reactions Leading To Tetrahydroindoles2.1 Ring Closure Reactions with N–C2 Bond Formation (a)2.2 Ring Closure Reactions with C2–C3 Bond Formation (b)2.3 Ring Closure Reactions with C3–C3a Bond Formation (c)2.4 Ring Closure Reactions with C7a–N Bond Formation (e)2.5 Ring Closure Reactions with C4–C5 Bond Formation (g)2.6 Ring Closure Reactions with C3a–C4 Bond Formation (h)3 Intermolecular Reactions Leading To Tetrahydroindoles3.1 Ring Closure Reactions with N–C2 + C3–C3a Bond Formation (ac)3.2 Ring Closure reactions with N–C2 + C7a–N Bond Formation (ae)3.3 Ring Closure reactions with C3–C3a + C7a–N Bond formation (ce)3.4 Ring Closure Reactions with N–C2, C3–C3a, and C7a–N Bond Formation (ace)4 Recovery Processes (Hydrogenation) of Indoles and Oxidation of Perhydroindoles in the Synthesis of 4,5,6,7-Tetrahydroindoles5 Conclusion

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“…yield in 2 stages. The spectroscopic data of synthetic (-)mesembrane ( 53) and (+)-crinane (55) are identical to the data for natural products.…”

Section: Review Synthesissupporting

confidence: 59%

Section: Intermolecular Reactions Leading To Tetrahydroindolesmentioning

confidence: 99%

Recent Advances in the Synthesis of Indoles with Partially Hydrogenated Benzene Ring (Tetrahydroindoles)

Mamedov,

Zhukova

2023

Synthesis

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“…Additionally, the synthesis of pyrroles 11 / 12 from oximes 2 and aryl-substituted alkynes 9 was investigated to allow for greater substitution around the pyrrole ring (Table ). Using a modification of Trofimov’s procedure, triphenylphosphine-catalyzed addition of keto-oximes 2 to acylacetylenes 9 gave a series of ester- and keto-substituted O -vinyloximes 10 . 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.…”

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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“…Expanding the scope of the pronucleophiles, Yavari and Trofimov both independently described alkyne Michael additions using oximes (Scheme ). , The oxygen center of the oxime motif serves as a good pronucleophile for phosphine-catalyzed Michael additions with mono- or disubstituted alkynes, leading to good yields.…”

Section: Nucleophilic Phosphine Catalysis Of Acetylenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Triphenylphosphine as an effective catalyst for ketoximes addition to acylacetylenes: regio- and stereospecific synthesis of (E)-(O)-2-(acyl)vinylketoximes

Cited by 20 publications

References 30 publications

Recent Advances in the Synthesis of Indoles with Partially Hydrogenated Benzene Ring (Tetrahydroindoles)

Recent Advances in the Synthesis of Indoles with Partially Hydrogenated Benzene Ring (Tetrahydroindoles)

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

Phosphine Organocatalysis

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