Synthesis of Azepane Derivatives by Silyl-aza-Prins Cyclization of Allylsilyl Amines: Influence of the Catalyst in the Outcome of the Reaction

Barbero, Asunción; Diez‐Varga, Alberto; Pulido, Francisco J.; González‐Ortega, Alfonso

doi:10.1021/acs.orglett.6b00538

Cited by 41 publications

(24 citation statements)

References 37 publications

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“…The first general approach towards the synthesis of azepanes by aza‐Prins cyclization has recently been published by our research group . Thus, silyl bis(homoallylic) amines react with aldehydes, in the presence of InCl 3 , to provide seven‐membered azacycles in high yields and with moderate to good diastereoselectivity in favour of the trans ‐2,7‐disubstituted derivatives.…”

Section: Synthesis Of Azacycles By Silyl‐prins Cyclizationmentioning

confidence: 99%

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Díez-Poza

Barbero

2017

Eur J Org Chem

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Prins cyclization has emerged as one of the most valuable methods for the construction of heterocycles. It proceeds through intramolecular addition of a π‐nucleophile to an oxocarbenium or related ion. The use of electron‐rich alkenes, such as allylsilanes (so‐called silyl‐Prins cyclization) offers the benefit of allowing more selective reactions. The regio‐ and stereochemical outcomes of these transformations are explained by well‐stablished transition states. This review presents the most important contributions involving silyl‐Prins cyclization to the stereoselective preparation of oxygen and nitrogen heterocycles. The influence of different structural variants in the selectivity of the cyclization is discussed. These reactions have frequently been used as key steps in the synthesis of a wide variety of natural products.

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Section: Synthesis Of Azacycles By Silyl‐prins Cyclizationmentioning

confidence: 99%

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Díez-Poza

Barbero

2017

Eur J Org Chem

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“…Some representatives of this class of azaheterocycles are known as antiviral agents, glycosidase inhibitors, anticancer agents, or antidiabetics. [9][10][11][12][13] Therefore, in view of their medicinal relevance, an increasing number of synthetic methods have been described in recent years for the construction of highly substituted azepine derivatives. [14][15][16][17][18] Also, pyrrole and its derivatives are among the most important nitrogen-containing heterocyclic compounds that exist in the structure of many natural products including bile pigments, heme, cytochromes, vitamin B 12 , and alkaloids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and investigation of antioxidant and antimicrobial activity of new pyrazinopyrroloazepine derivatives using Fe₃O₄/CuO/ZnO@MWCNT MNCs as organometallic nanocatalyst by new MCRs

Amiri

Hossaini

Azizi

2022

Applied Organom Chemis

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In this study, we synthesized pyrazinopyrroloazepine derivatives in high yields using multicomponent reactions of isatoic anhydride, N‐methylimidazole, alkyl bromides, activated acetylenic compounds, ethyl glycinate and methyl aziridine in the presence of Fe3O4/CuO/ZnO@MWCNT as a high performance catalyst in water at room temperature. The Fe3O4/CuO/ZnO@MWCNT synthesizes using Petasites hybridus rhizome water extract as a green media and moderate base. As well Fe3O4/CuO/ZnO@MWCNT MNCs show a good improvement in the yield of the product and displayed significant reusable activity. Investigation of antioxidant ability of synthesized compounds using radical trapping of diphenyl‐picrylhydrazine (DPPH) and ferric reduction power experiment is another purpose in this research. Because of having two NH groups in the synthesized compounds, these compounds shown the good antioxidant activity relative two standards. Compound 7c was shown excellent antioxidant activity. Also, the antimicrobial activity of some synthesized compounds proved by employing the disk diffusion test on gram‐positive and gram‐negative bacteria. The pyrazinopyrroloazepines 7a, 7c, 7d and 7f have the maximum effect on Escherichia coli compared with gram‐positive and gram‐negative bacteria because of good inhibition zone diameter. This procedure has some benefits such as short reaction time, product with excellent yields, simple catalyst and products separation.

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“…During many years, our research group has been interested in the synthesis of carbo- [ 13 , 14 ] and heterocycles [ 15 , 16 ] using the chemistry of organosilanes. At this point, we thought that it would be interesting to study the independent effect of both silicon and alkyl groups in the acid-catalyzed cyclization of δ,γ-epoxy alcohols.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

Díez-Poza

Barbero

2021

Molecules

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The regioselective ring opening of epoxy alcohols is an effective method for the synthesis of different types of oxacycles. The 5-exo opening being preferred vs. the 6-endo mode, according to Baldwin rules, the use of silyl-substituted oxiranes has been reported as a possible method to favor the 6-endo cyclization. However, there is a need for a detailed study on the different factors (structural factors, catalyst nature or conditions) that influence this process. In this paper, the acid-catalyzed cyclization of epoxysilyl alcohols was studied, focusing on the effect of substituents and reaction conditions on the outcome of the process. Two types of heterocycles (tetrahydrofurans or tetrahydropyrans) were selectively obtained depending on the structure of the initial epoxysilyl alcohol. Interestingly, cyclization of hindered epoxysilyl alcohols mainly proceeds through an unexpected side reaction, which implies a previous isomerization to an aldehyde. A mechanistic proposal for the formation of the different products is presented.

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Synthesis of Azepane Derivatives by Silyl-aza-Prins Cyclization of Allylsilyl Amines: Influence of the Catalyst in the Outcome of the Reaction

Cited by 41 publications

References 37 publications

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Synthesis and investigation of antioxidant and antimicrobial activity of new pyrazinopyrroloazepine derivatives using Fe₃O₄/CuO/ZnO@MWCNT MNCs as organometallic nanocatalyst by new MCRs

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

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Synthesis of Azepane Derivatives by Silyl-aza-Prins Cyclization of Allylsilyl Amines: Influence of the Catalyst in the Outcome of the Reaction

Cited by 41 publications

References 37 publications

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Synthesis and investigation of antioxidant and antimicrobial activity of new pyrazinopyrroloazepine derivatives using Fe3O4/CuO/ZnO@MWCNT MNCs as organometallic nanocatalyst by new MCRs

Influence of the Substituents on the Opening of Silylepoxy Alcohols: 5-exo-Cyclization towards Tetrahydrofurans vs. Unexpected Side Reaction Leading to Tetrahydropyrans

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Synthesis and investigation of antioxidant and antimicrobial activity of new pyrazinopyrroloazepine derivatives using Fe₃O₄/CuO/ZnO@MWCNT MNCs as organometallic nanocatalyst by new MCRs