Retention of Symmetry Versus Desymmetrization for Bicyclo[2.2.2]octenes in the Presence of a Bridgehead Amide Group

Hren, Jure; Perdih, Franc; Polanc, Slovenko; Kočevar, Marijan

doi:10.1002/ejoc.201100104

Cited by 5 publications

(5 citation statements)

References 36 publications

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“…We found that such conditions (analogous to those used previously) [31,32] were not adequate to achieve quantitative conversion into the products 5; indeed, the only way to achieve this was to apply higher reaction temperatures (140-180°C). However, in order to reach temperatures above 120°C while keeping the pressure below the upper limit [as the boiling point of the neat ethyl vinyl ether (2) is rather low (33°C)], it was necessary to add some appropriate additives to decrease the vapor pressure, such as ionic liquids (e.g., [bmim]BF 4 ) or n-butanol (which, due to the easier isolation of the products, proved to be preferable) [47][48][49][50].…”

Section: Resultsmentioning

confidence: 99%

Diels–Alder reaction of fused pyran-2-ones with ethyl vinyl ether

et al. 2012

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Ethyl vinyl ether was found to be an appropriate synthetic equivalent of acetylene for a set of Diels-Alder reactions with fused pyran-2-ones that yield fused carbocyclic systems. Transformations were conducted under microwave irradiation with DABCO (as a catalyst for the elimination of ethanol) and with n-butanol as the additive. A single-crystal X-ray diffraction structure is presented for N-(5,6,7,8-tetrahydro-6-methyl-8-oxonaphthalen-2-yl)benzamide.

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Section: Resultsmentioning

confidence: 99%

Diels–Alder reaction of fused pyran-2-ones with ethyl vinyl ether

et al. 2012

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“…An effective intramolecular hydrogen bonding between the N–H proton and the C-2 carbonyl group to form a 6-membered ring renders the latter more electrophilic and consequently more reactive toward the nucleophiles (Figure ). This has been supported by an independent experiment with the N -methyl derivative 10a , prepared by the methylation of 5a with dimethyl sulfate under basic conditions and shown in Scheme . Under the same hydrolytic reaction conditions as for 5a , the N -methyl derivative 10a afforded a complex mixture of products.…”

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confidence: 78%

Regioselective Hydrolysis and Transesterification of Dimethyl 3-Benzamidophthalates Assisted by a Neighboring Amide Group

et al. 2016

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An efficient, highly regioselective hydrolysis and transesterification of dimethyl 3-benzamidophthalates into the corresponding carboxylic acid monoesters and mixed esters (including tert-butyl esters) under basic conditions is presented. The selectivity is governed by the neighboring 3-benzamido moiety's participation and by the nature of the solvent. In alcohols the reaction occurred exclusively at the ortho-position to the benzamido functionality, in pyridine or acetonitrile at both ester groups. An insight into the mechanistic pathway was obtained from a (1)H NMR study in perdeuteromethanol.

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“…55 Base-catalyzed isomerization of these tetraesters 86 takes place with the retention of symmetry and yields the products 87 that are appropriate substrates for catalytic hydrogenation. This hydrogenation proceeds under far milder conditions (5 h at room temperature, 3 bar of H 2 and with standard Pd/C as the catalyst) as were necessary for the above mentioned bicyclo[2.2.2]octenes 82 (analogous to those before the isomerization) indicating that the isomerization (86 → 87) strongly decreases the steric hindrance around the double bond.…”

Section: Scheme 24mentioning

confidence: 99%

Regio- and stereoselective syntheses and cycloadditions of substituted 2H-pyran-2-ones and their fused derivatives

Kranjc¹,

Kočevar²

2013

Arkivoc

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Microwave-assisted conditions have been shown to be very efficient for the synthesis of a variety of compounds containing 2H-pyran-2-one skeleton that plays important roles in nature and in synthetic chemistry. Furthermore, such compounds (especially those incorporating a 3-acylamino group) were shown to be efficient partners for the Diels-Alder reactions with a variety of dienophiles including acetylene derivatives, maleic anhydride, substituted maleimides, vinyl-moiety-containing dienophiles, as well as (Z)-1-methoxybut-1-en-3-yne. Reactions were carried out under conventional thermal conditions, microwave irradiation and under high pressure (13-15 kbar) and resulted in a plethora of different product types: anilines, bi-and terphenyls, indoles, isoindoles, 2-oxabicyclo[2.2.2]oct-5-enes and bicyclo[2.2.2]octenes. Many of the transformations showed remarkable regio-and stereoselectivity, depending primarily on the substitution patterns of the reactants and reaction conditions applied.

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Retention of Symmetry Versus Desymmetrization for Bicyclo[2.2.2]octenes in the Presence of a Bridgehead Amide Group

Abstract: Keywords: Isomerization / Ionic liquids / Green chemistry / Microwave chemistry / Bicyclic compounds An efficient, microwave-assisted and ionic-liquid-catalyzed esterification of bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride derivatives into the corresponding

Cited by 5 publications

References 36 publications

Diels–Alder reaction of fused pyran-2-ones with ethyl vinyl ether

Diels–Alder reaction of fused pyran-2-ones with ethyl vinyl ether

Regioselective Hydrolysis and Transesterification of Dimethyl 3-Benzamidophthalates Assisted by a Neighboring Amide Group

Regio- and stereoselective syntheses and cycloadditions of substituted 2H-pyran-2-ones and their fused derivatives

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