Transanulare Wechselwirkungen in difunktionellen mittleren Ringen, 4. Spektroskopische und theoretische Untersuchungen an bicyclischen Boraalkenen

Rademacher, Paul; Wiesmann, Reinhard F.

doi:10.1002/cber.19941270309

Cited by 9 publications

(3 citation statements)

References 48 publications

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“…For a product study, 6-OTs was solvolyzed in methanol and TFE buffered with 2,6-lutidine. Gas chromatography indicated that the products were 2-bicyclo[3.2.2]nonene ( 10 ), 2-bicyclo[3.3.1]nonene ( 11 ), ,, tricyclo[3.3.1.0 2,8 ]nonane ( 12 ), 2-R-bicyclo[3.2.2]nonane [ 6-R : 6-OMe (R = OMe), 6-OTFE (R = OCH 2 CF 3 )], exo -2-R-bicyclo[3.3.1]nonane [ 8-R : 8-OMe (R = OMe), 8-OTFE (R = OCH 2 CF 3 )], and a small amount of an unidentified ether (Scheme ). The yields of the products are shown in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Authentic 2-Bicyclo[3.3.1]nonene (11). 11 was prepared by a method similar to that reported in the literature. ,, In the reported 13 C NMR data 20 one carbon signal was missing. The complete data follow: 13 C NMR (CDCl 3 , 67.8 MHz) δ 130.5 (CH), 129.4 (CH), 34.2 (CH 2 ), 32.4 (CH 2 ), 31.8 (CH 2 ), 29.6 (CH), 29.2 (CH 2 ), 27.2 (CH), 18.2 (CH 2 ).…”

Section: Methodsmentioning

confidence: 99%

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Solvolysis of 2-Bicyclo[3.2.2]nonyl p-Toluenesulfonate. Evidence for the Formation of Classical Carbocation Intermediates

et al. 2000

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The solvolysis rate of 2-bicyclo[3.2.2]nonyl p-toluenesulfonate (6-OTs) was nearly equal to that of cycloheptyl p-toluenesulfonate in 2,2,2-trifluoroethanol (TFE). This indicates that the ethylene bridge in 6-OTs does not significantly enhance the rate and that 6-OTs ionizes without anchimeric assistance. The solvolysis of [1-(13)C]-2-bicyclo[3.2.2]nonyl p-toluenesulfonate in methanol or TFE gave 2-substituted bicyclo[3.2.2]nonane, exo-2-substituted bicyclo[3.3.1]nonane, 2-bicyclo[3.2.2]nonene (10), and 2-bicyclo[3.3.1]nonene (11), whose distributions of (13)C labels were determined by quantitative (13)C NMR analysis using a relaxation reagent. The (13)C labels were exclusively placed at only two positions, the ratios of them were not unity, and the labels in 10 were less extensively scrambled than those in other products. These results indicate that the 2-bicyclo[3.2.2]nonyl cation is classical and that 10 is formed at a former ionization stage than 2-substituted bicyclo[3.2.2]nonane. The (13)C redistributions for both exo-2-substituted bicyclo[3.3.1]nonane and 11, which are yielded via 1,3-hydride shift, were similar to that of 2-substituted bicyclo[3.2.2]nonane, suggesting that 1,3-hydride shift occurs mainly at the solvent-separated ion pair.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Solvolysis of 2-Bicyclo[3.2.2]nonyl p-Toluenesulfonate. Evidence for the Formation of Classical Carbocation Intermediates

et al. 2000

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“…During the solvolysis study of 2-bicyclo[3.2.2]nonyl p -toluenesulfonates, Okazaki's group and Schafaer's team found that the solvolysis products of such bicycles are usually enriched with bicyclo[3.3.1]nonanes. 221–224 It was found that when 477 was solvolyzed in methanol and 2,2,2-trifluoroethanol (TFE) buffered with 2,6-lutidine, 2-bicyclo[3.3.1]nonene ( 479 ) (yield 15–47%) and exo -2-R-bicyclo[3.3.1]nonane (R = methoxy, 480 ; R = trifluoroethoxy, 481 ) were formed along with other bicycles in 12–23% yield. The solvolytic data indicated that these products were formed from the 2-bicyclo[3.2.2]nonyl cation ( 478 ), thereby unveiling the evidences for the formation of a classical carbocation intermediate (Scheme 110).…”

Section: Synthetic Approachesmentioning

confidence: 99%

Different routes for the construction of biologically active diversely functionalized bicyclo[3.3.1]nonanes: an exploration of new perspectives for anticancer chemotherapeutics

et al. 2023

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Spectroscopic and Theoretical Investigations of Monocyclic Dioximes and Dimethoximes with Six-, Eight-, and Ten-Membered Rings

Strenge

Rademacher²

1999

Eur. J. Org. Chem.

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The dioximes 4–6 and the dimethoximes 7–9, which contain the functional groups in opposite positions of a six‐, eight‐, or ten‐membered ring, were synthesized. Their conformational properties and transannular interactions were investigated by spectroscopic (PE, 13C NMR) and theoretical (MMX, AM1, ab initio HF, and B3LYP) methods. While the cyclooctane derivatives 5 and 8 have conformations favourable for through‐space interactions of the π(CN) orbitals, in the other compounds no such interactions can be ascertained. Through‐space orbital interactions in the molecules with an eight‐membered ring lead to a splitting of the π(CN) MOs of 0.4 eV.

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Transanulare Wechselwirkungen in difunktionellen mittleren Ringen, 4. Spektroskopische und theoretische Untersuchungen an bicyclischen Boraalkenen

Cited by 9 publications

References 48 publications

Solvolysis of 2-Bicyclo[3.2.2]nonyl p-Toluenesulfonate. Evidence for the Formation of Classical Carbocation Intermediates

Solvolysis of 2-Bicyclo[3.2.2]nonyl p-Toluenesulfonate. Evidence for the Formation of Classical Carbocation Intermediates

Different routes for the construction of biologically active diversely functionalized bicyclo[3.3.1]nonanes: an exploration of new perspectives for anticancer chemotherapeutics

Spectroscopic and Theoretical Investigations of Monocyclic Dioximes and Dimethoximes with Six-, Eight-, and Ten-Membered Rings

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