ChemInform Abstract: RK.‐FAEHIGKEIT VON OXIRANEN SUBSTITUIERTER NORBORNENE

Malinovskii, M. S.; Kas’yan, L. I.; Ovsyanik, V. D.; Sil'chenko, L. A.

doi:10.1002/chin.197338180

Cited by 2 publications

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“…Methanolysis of epoxy derivatives 88 and 89 in alkaline medium [81,82] occurs in a similar way, while the reaction with methanol in acid medium is accompanied by demethylation during heterocyclization, as in the methanolysis of compound 91 [83,84] 1,3-Dioxolanes are known transformation products of epoxy compounds, which are formed in the presence of Lewis acids [86,87]. Barkhash and co-workers performed reactions of 4β,5α-epoxy derivative of cariophyllene (92) with carbonyl compounds, such as acrolein, crotonaldehyde, α-methylacrolein, and acetone, over clay; the authors also isolated related diols which were formed from compound 92 in the absence of aldehydes over the same catalyst [90] (Scheme 52). Dioxolanes were obtained from epoxy derivatives of acyclic [4] and alicyclic alkenes [90], spiro compounds [91], etc.…”

Section: Methodsmentioning

confidence: 99%

“…In the recent years, ruthenium [88] and titanium compounds [89] were successfully used as catalysts. An example of formation of diol as the only product of the reaction of substituted epoxynorbornane with acetone was reported in [92]. Barkhash and co-workers performed reactions of 4β,5α-epoxy derivative of cariophyllene (92) with carbonyl compounds, such as acrolein, crotonaldehyde, α-methylacrolein, and acetone, over clay; the authors also isolated related diols which were formed from compound 92 in the absence of aldehydes over the same catalyst [90] (Scheme 52).…”

Section: Methodsmentioning

confidence: 99%

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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: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Transformation of oxiranes into other oxygen-containing heterocyclic systems

2004

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“…viously [2], and their reduction [3], hydrolysis [4], and epoxidation with peroxy acids [5] were studied. N-Acyl derivatives of bicyclic amines IIa and IIb were synthesized by the action of acyl chlorides [6,7] and anhydrides [8]; in addition, their stereochemical behavior [9], alkylation [10], reduction [6,7], and epoxidation [9] were reported.…”

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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: RK.‐FAEHIGKEIT VON OXIRANEN SUBSTITUIERTER NORBORNENE

Cited by 2 publications

References 0 publications

Transformation of oxiranes into other oxygen-containing heterocyclic systems

Transformation of oxiranes into other oxygen-containing heterocyclic systems

Amides containing two norbornene fragments. Synthesis and chemical transformations

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