Equilibrium and Isomerization in Bicyclic Nitriles<sup>1</sup>

Wilder, Pelham; Knight, David B.

doi:10.1021/jo01020a046

Cited by 17 publications

(7 citation statements)

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“…In accordance with the literature [7] the reduction is accompanied by epimerization; the presence of an impurity (ϳ5%) of the corresponding exo-stereoisomer has been revealed by the 1 H NMR spectrum. A number of sulfonamides (7a-j) have been obtained from the amine (5) by the action of aromatic sulfonylchlorides; high product yields have been achieved when the reaction was carried out in heterogeneous medium and with an equimolar ratio of the reagents.…”

Section: Results and Discussion Chemical And Spectral Investigationssupporting

confidence: 90%

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Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

et al. 1997

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Section: Results and Discussion Chemical And Spectral Investigationssupporting

confidence: 90%

“…Epoxidation of amines of the norbornene series has not been given any special attention, and this is the reason why 4-azatricyclo [4.2.1.0 3,7 ]nonanes of type 3 are so rarely found in the literature. It is reported in Ref.…”

Section: Introductionmentioning

confidence: 99%

Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

et al. 1997

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“…Epimerization of 5-9% of the endo-isomer was observed in the reaction; the exo-amine (7a) was isolated in a pure state [9].…”

Section: Results and Discussion: Chemical And Spectral Investigationsmentioning

confidence: 97%

Azabrendanes. III. Synthesis of stereoisomeric exo‐ and endo‐5‐acylaminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1]heptanes and their reduction by lithium aluminum hydride

Kas’yan¹,

Tarabara²,

Savel'yeva³

et al. 2001

Heteroatom Chemistry

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A number of stereoisomeric N‐[aryl(alkyl, cycloalkyl)carbonyl]‐exo(endo)‐5‐aminomethylbicyclo[2.2.1]hept‐2‐enes have been synthesized from bicyclo[2.2.1]hept‐2‐en‐exo(endo)‐5‐carbonitrile via reduction of the latter by lithium aluminum hydride and subsequent reactions of the resulting amines with aryl(alkyl, cycloalkyl)carbonyl chlorides and anhydrides. The direction of reaction of amides with peroxy acids does not depend on orientation of substituents in the bicyclic fragment: that is, for both exo‐ and endo‐isomers the epoxidations are completed by the formation of N‐[aryl(alkyl, cycloalkyl)carbonyl]‐exo(endo)‐5‐aminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1] heptanes. The reduction of stereoisomeric epoxides by lithium aluminium hydride proceeds in different directions; that is, isomers with an exo‐oriented amido group form the substituted exo‐5‐alkylaminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1]heptanes and the reactions of epoxides of endo‐amides are accompanied by intramolecular cyclization and completed by the formation of N‐[aryl(alkyl, cycloalkyl)]‐exo‐2‐hydroxy‐4‐azatricyclo[4.2.1.03,7]nonanes. The structures and stereochemical homogenity of the products have been confirmed by the analysis of 1H and 13C NMR spectra, correlation spectroscopy, and nuclear Overhauser enhancement spectroscopy experiments. We discuss the behavior of epoxides and provide an analysis of the coefficients of the atomic orbitals in the molecular orbital–linear combination of atomic orbitals equation (AM1 method). © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:119–130, 2001

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“…Carbonitriles 3a, 3b gave exoand endo-5-aminomethylbicyclo[2.2.1]hept-2-enes 2a, 2b upon treatment with the lithium aluminum hydride (LAH). Whilst reduction of exo-carbonitrile 3a gave exoamine 2a as the sole product, the reduction of endonitrile 3b was accompanied by epimerization and the formation of 6-9% admixture of amine 2a [17].…”

Section: Synthesis Of Ureasmentioning

confidence: 99%

Azabrendanes V. Synthesis and reactions of stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-ene-based ureas

Kas’yan

Kas’yan²,

Tarabara

et al. 2008

Open Chemistry

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Equilibrium and Isomerization in Bicyclic Nitriles¹

Cited by 17 publications

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Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

Azabrendanes. III. Synthesis of stereoisomeric exo‐ and endo‐5‐acylaminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1]heptanes and their reduction by lithium aluminum hydride

Azabrendanes V. Synthesis and reactions of stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-ene-based ureas

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Equilibrium and Isomerization in Bicyclic Nitriles1

Cited by 17 publications

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Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

Azabrendanes. I. Synthesis, structure and spectral parameters of N-(arylsulfonyl)-exo-2-hydroxy-4-azatricyclo[4.2.1.03,7]nonanes

Azabrendanes. III. Synthesis of stereoisomeric exo‐ and endo‐5‐acylaminomethyl‐exo‐2,3‐epoxybicyclo[2.2.1]heptanes and their reduction by lithium aluminum hydride

Azabrendanes V. Synthesis and reactions of stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-ene-based ureas

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Equilibrium and Isomerization in Bicyclic Nitriles¹