[n]Staffanes: the parent hydrocarbons

Murthy, G. Sreenivasa; Hassenrück, Karin; Lynch, Vincent M.; Michl, Josef

doi:10.1021/ja00200a057

Cited by 28 publications

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“…This effect is contributed to the increased s character of the exocyclic bond (Bent's rule) and is even visible in the oligoBCP compounds 41 and 42 , so‐called n ‐staffanes (Figure ). Here, the distance between the two bridgehead carbon atoms increases with the amount of additional BCP‐monomer units . The same effect results in rather long internal distances for alkyl‐ and aryl‐substituted BCPs .…”

Section: Physical Propertiesmentioning

confidence: 80%

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Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Locke

Bernhard

Senge

2019

Chemistry A European J

189

143

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Nonconjugated hydrocarbons, like bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, triptycene, and cubane are a unique class of rigid linkers. Due to their similarity in size and shape they are useful mimics of classic benzene moieties in drugs, so‐called bioisosteres. Moreover, they also fulfill an important role in material sciences as linear linkers, in order to arrange various functionalities in a defined spatial manner. In this Review article, recent developments and usages of these special, rectilinear systems are discussed. Furthermore, we focus on covalently linked, nonconjugated linear arrangements and discuss the physical and chemical properties and differences of individual linkers, as well as their application in material and medicinal sciences.

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Section: Physical Propertiesmentioning

confidence: 80%

“…Here, the distance betweent he two bridgehead carbon atoms increasesw ith the amount of additional BCP-monomeru nits. [75] The same effect results in rather long internal distances for alkyl-and aryl-substituted BCPs. [76] On the other hand, the opposite effect occurs in quaternary pyridinium salts 43.…”

Section: Molecular Formulamentioning

confidence: 99%

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Locke

Bernhard

Senge

2019

Chemistry A European J

189

143

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“…This lack of polymerizability of 1 under the anionic conditions is probably due to the high electron density of the carbon-carbon bond in the [3.3.1]propellane monomer, while the anionic polymerization of several [1.1.1]propellane derivatives has been reported. [3][4][5][6] We have thus clarified that the thermal or the cationic polymerization of 1 proceeds to provide the poly(1) in a good to quantitative yield, while its poor solubility still prohibits further characterization. [13] We next employed monomer 2, another 1,3-dehydroadamantane derivative possessing the flexible butyl substituent, for the various polymerizations.…”

Section: Resultsmentioning

confidence: 99%

“…Only the ring-opening polymerization of several [1.1.1]propellane derivatives has been so far reported. [3][4][5][6] 1,3-Dehydroadamantane, 1, has a framework of [3.3.1]propellane. [7,8] This hydrocarbon possessing a strained cyclopropane ring can be synthesized from 1,3-dibromoadamantane in a good yield and shows a sufficient stability even after the isolation.…”

Section: Introductionmentioning

confidence: 99%

Cationic Ring‐Opening Polymerization of 1,3‐Dehydroadamantanes

Matsuoka

Ogiwara

Uehara

et al. 2006

Macromolecular Symposia

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Summary: Ring-opening polymerizations of [3.3.1]propellane derivatives, 1,3-dehydroadamantane (1) and 5-butyl-1,3-dehydroadamantane (2), were carried out with CF 3 SO 3 H in CH 2 Cl 2 at 0 8C for 6-42 h. The central s-bonds in 1 and 2 were exclusively opened to afford novel poly ([3.3.1]propellane)s, poly(1,3-adamantane)s, in 52-95% yields. The resulting poly(2) possessing flexible butyl substituent was soluble in chloroform, THF, and 1,2-dichlorobenzene, and the degree of polymerization was estimated to be greater than 30, while the poly(1) was hardly soluble in the common organic solvents. All aliphatic poly(1) and poly(2) showed high thermal stability, their 10% weight loss temperatures were 421 and 486 8C, respectively.

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“…The 13 C chemical shifts of the methylene carbons (C2) of the various products were unambiguously assigned by additivity methodology utilizing appropriate 13 C SCS data (Cl, 6.09 ppm; CF 3 , −2.26 ppm; COOCH 3 , 0.56 ppm). The calculated values for the dimers were determined from the 13 C chemical shift data for the parent [2]-staffane . The relevant NMR data for the reactions of the various acids in CDCl 3 and CD 2 Cl 2 are listed in Table .…”

Section: Methodsmentioning

confidence: 98%

Manifestations of Bridgehead−Bridgehead Interactions in the Bicyclo[1.1.1]pentane Ring System

et al. 1999

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A series of 3-halo-substituted bicyclo[1.1.1]pentane-1-carboxylic acids 1 (Y = COOH; X = F, Cl, Br, I, and CF(3)) as well as the parent compound 1 (Y = COOH, X = H) have been prepared, and a study of some of their properties have been made. It was found that their reactions with xenon difluoride cover a wide range of reactivities. On one hand, the fluoro acid 1 (Y = COOH, X = F) displayed no apparent reaction at all while, on the other, the bromo acid 1 (Y = COOH, X = Br) and parent compound 1 (Y = COOH, X = H) underwent ready reaction with complete disintegration of the ring system. A possible explanation is advanced based on polar kinetic and thermodynamic effects governing the lifetime of an intermediate acyloxy radical species. The relative ease of oxidation of the carboxylates 1 (Y = COO(-); X = H, F, Cl, Br, I, CF(3), and COOCH(3)), as mirrored by their peak oxidation potential values (E(p)) determined by cyclic voltammetry, also covers a wide range. These data coupled with the dissociation constants (pK(a)) of some of the acids 1 (Y = COOH; X = H, F, Cl, and CF(3)) reflect significantly on the modes of transmission of electronic effects acting through the bicyclo[1.1.1]pentane ring system.

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[n]Staffanes: the parent hydrocarbons

Cited by 28 publications

References 0 publications

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Cationic Ring‐Opening Polymerization of 1,3‐Dehydroadamantanes

Manifestations of Bridgehead−Bridgehead Interactions in the Bicyclo[1.1.1]pentane Ring System

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