ChemInform Abstract: ISOMERISIERUNG EINIGER SUBSTITUIERTER NORBORNENE

Malinovskii, M. S.; Kas’yan, L. I.; Ovsyanik, V. D.

doi:10.1002/chin.197408215

Cited by 3 publications

(4 citation statements)

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“…The crucial role of stereochemical factor in the formation of lactones is illustrated by ready enzymatic hydrolysis of one of the two stereoisomeric esters 133 and 134, which leads to lactone 135 [115] (Scheme 68 γ-hydroxy-δ-lactones Lactones were also obtained by transformation of γ,δ-epoxy esters in acid medium [116]. Participation of amide groups in the formation of lactone rings was reported for bicyclic systems 138 (R = H, Me) in reactions with peroxy acids [2,10,[117][118][119]. In each case, the cyclization is favored by stereochemical factor, i.e., by the possibility for rear attack by nucleophile at the oxirane carbon atom.…”

Section: Transformations Of Oxiranes Into Lactones and Alkylene Cmentioning

confidence: 99%

Transformation of oxiranes into other oxygen-containing heterocyclic systems

2004

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The review analyzes published data on the transformations of epoxy derivatives into other oxygencontaining heterocyclic systems, such as cyclic ethers (including cage-like structures), dioxolanes, ortho esters, lactones, and cyclic carbonates, some of which occur in the nature and exhibit biological activity. Reaction mechanisms involving heterolytic, homolytic, enzymatic, and single-electron transfer processes, as well as [2+2]-and [3+3]-cycloadditions, are discussed.

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Section: Transformations Of Oxiranes Into Lactones and Alkylene Cmentioning

confidence: 99%

Transformation of oxiranes into other oxygen-containing heterocyclic systems

2004

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“…4 Nucleophilic groups, for example, a hydroxy group, present in the rear endo-area are often involved in epoxidation giving rise to cyclisation products. 145,192,193 This is due to the favourable arrangement of the nucleophile in the area of antibonding p*-molecular orbital of the epoxide ring being formed. In accordance with the Kerten ± Hammett principle, the possibility of realisation of molecular conformations, convenient for the formation of activated complexes, is especially significant in this case.…”

Section: Intramolecular Cyclisation In Reactions Of Substituted Norbo...mentioning

confidence: 99%

“…The corresponding exo-stereoisomers are readily converted into epoxides. 173,174 The formation of similar heterocyclic derivatives containing other heteroatoms has been little studied. Formation of epoxide from unsaturated sulfone has been reported.…”

Section: Intramolecular Cyclisation In Reactions Of Substituted Norbo...mentioning

confidence: 99%

Epoxidation of substituted norbornenes. Stereochemical aspects and accompanying intramolecular transformations

Kas’yan¹

1998

Russ. Chem. Rev.

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“…The stereoisomers were separated by fractional distillation [15]. For the synthesis of acyl chlorides IVa and IVb we selected conditions which prevented isomerization of the products [17]. For the synthesis of acyl chlorides IVa and IVb we selected conditions which prevented isomerization of the products [17].…”

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confidence: 99%

Amides containing two norbornene fragments. Synthesis and chemical transformations

et al. 2004

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Reactions of stereochemically pure bicyclo[2.2.1]hept-5-en-exo-and endo-2-ylmethylamines with bicyclo[2.2.1]hept-2-ene-5-carbonyl chlorides gave the corresponding carboxamides having two norbornene fragments. Their conformations and steric strains were studied by the MM2 molecular mechanics method, and electron density distribution in their molecules was determined by PM3 quantum-chemical calculations. The results of calculation of the energy of activation for epoxidation of the dienes in the gas phase and in solution (COSMO) showed that chemoselective oxidation of only one double bond therein is impossible. The corresponding diepoxy derivatives were synthesized by oxidation of the dienes with peroxyacetic acid; the oxidation of amides with endo orientation of the carbonyl group was accompanied by heterocyclization with formation of exo- 2-hydroxy-4-oxatricyclo[4.2.1.0 3,7 ]nonan-5-one. Reduction of the amides and their epoxy derivatives with lithium tetrahydridoaluminate afforded the corresponding secondary amines possessing two cage-like fragments; the reduction products were functionalized at the nitrogen atom by treatment with p-nitrobenzenesulfonyl chloride and p-toluenesulfonyl isocyanate. The structure of the prepared compounds was confirmed by the IR and 1 H and 13 C NMR spectra. IIaAmine 2.73, 2.59 5.96, 6.03 3 J 2, 3 = 6.0, 3 J 2, 1 = 2.8, 3 J 3, 4 = 2.8 1.35 1.14 2 J exo-6, endo-6 = 11.3, 3 J exo-6, 1 = 8.0 1.04 3 J endo-6, 5 = 3.6 1.14, 1.22 2.65 1.13 IIb Amine 2.81, 2.72 5.86, 6.07 3 J 2, 3 = 5.8, 3 J 2, 1 = 2.8, 3 J 3, 4 = 3.0 2.03 1.75 2 J exo-6, endo-6 = 11.4, 3 J exo-6, 5 = 9.2, 3 J exo-6, 1 = 3.9 0.42 3 J endo-6, 5 = 4.1, 4 J endo-6, syn-7 = 2.6 1.37, 1.18 2 J syn-7, anti-7 = 7.9 2.37, 2.29 2 J 8A, 8B = 12.2, 3 J 8A, 5 = 7.3, 3 J 8B, 5 = 8.2 Vc Amine 2.81 6.16, 5.96 3 J 2, 3 = 3.0, 3 J 2, 1 = 2.4, 3 J 3, 4 = 2.7 2.20 1.84 2 J exo-6, endo-6 = 12.6, 3 J exo-6, 5 = 9.0, 3 J exo-6, 1 = 3.9 0.54 3 J endo-6, 5 = 3.0, 4 J endo-6, syn-7 = 2.2 1.42, 1.27 2 J syn-7, anti-7 = 8.1 2.95, 3.03 2 J 8A,8B = 13.5, 3 J 8A, 5 = 7.2, 3 J 8B, 5 = 5.7 VIa Acid 2.88, 2.85 6.06, 6.01 3 J 2, 3 = 5.5, 3 J 2, 1 = 3.0, 3 J 3, 4 = 3.0 1.95 1.27 2 J exo-6, endo-6 = 11.1, 3 J exo-6, 5 = 8.5, 3 J exo-6, 1 = 2.5 1.88 3 J endo-6, 5 = 3.7, 4 J endo-6, syn-7 = 3.7 1.32, 1.68 2 J syn-7, anti-7 = 8.4 a 4.39, 4.34 a 5.79 VIb Acid 2.92, 3.16 6.23, 5.98 2.91 1.93 2 J exo-6, endo-6 = 12.8, 3 J exo-6, 5 = 9.4, 3 J exo-6, 1 = 3.8 1.41 3 J endo-6, 5 = 4.0, 4 J endo-6, syn-7 = 2.7 1.46, 1.29 2 J syn-7, anti-7 = 7.9 a 4.43, 4.35 a 6.02 a Benzyl CH 2 group. VIIa Amine 2.57, 2.25 3.00-3.10 1.60 1.36 2 J exo-6, endo-6 = 11.5, 3 J exo-6, 5 = 8.4, 3 J exo-6, 1 = 2.4 1.05 1.25, 0.81 2 J syn-7, anti-7 = 10.2 3.00-3.10 5.72 Acid 2.47, 2.41 3.00-3.10 2.08 1.64 2 J exo-6, endo-6 = 12.4 1.20 1.39, 1.18 2 J syn-7, anti-7 = 8.3 --VIIc Amine 2.51, 2.48 3.28, 3.09 3 J 2, 3 = 3.0 1.50 1.73 2 J exo-6, endo-6 = 12.7, 3 J exo-6, 5 = 10.7, 3 J exo-6, 1 = 4.3 0.81 3 J endo-6, 5 = 4.9, 4 J endo-6, syn-7 = 2.3 1.37, 0.76 2 J syn-7, anti-7 = 10.0 3.20-3.32 2 J 8A,...

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ChemInform Abstract: ISOMERISIERUNG EINIGER SUBSTITUIERTER NORBORNENE

Abstract: Die Reaktion der Norbomencarbonsäure (I) mit SOCl2 und nachfolgend Anilin bzw. Diäthylamin liefert Gemische der exo‐ (II) und endo‐Amide (III).

Cited by 3 publications

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Transformation of oxiranes into other oxygen-containing heterocyclic systems

Transformation of oxiranes into other oxygen-containing heterocyclic systems

Epoxidation of substituted norbornenes. Stereochemical aspects and accompanying intramolecular transformations

Amides containing two norbornene fragments. Synthesis and chemical transformations

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