[5]Metacyclophane

Straten, J. W. Van; Wolf, W. H. De; Bickelhaupt, F.

doi:10.1016/s0040-4039(01)83596-6

Cited by 46 publications

(9 citation statements)

References 7 publications

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“…The supernatant solution was removed and hydrolyzed; it contained 10% diphenylmagnesium [according to the titration for Mg 2ϩ and OH Ϫ (acid/ Interestingly, the intra-annular aromatic xylylene protons ArЈH are deshielded by 0.4 ppm. This is reminiscent of analogous behavior of aryl protons inside the cavity of small metacyclophanes; [20,21] it has been ascribed to the van der Waals effect caused by steric congestion. [22] As similar changes have also been observed for 6 [9] and 7, [11] these phenomena are indicative of the rotaxane-type threading of a diarylmagnesium into a m-xylylene crown ether cavity.…”

Section: Complexation Of 8 With Diarylmagnesium Compoundsmentioning

confidence: 83%

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

et al. 2003

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The interaction between the title compound, bis(coronand) 8, and the diarylmagnesium compounds Ph 2 Mg and (ptBuC 6 H 4 ) 2 Mg in diethyl ether leads to the formation of 1:2 complexes (9 and 10, respectively), irrespective of the initial ratio of the components. In [D 8 ]toluene, the three complex types can be discerned by 1 H NMR spectroscopy: double side-on (9a, 10a), side-on/rotaxane (9b, 10b), and, to a very minor extent, double rotaxane (9c, 10c). In the case of 10a and 10b, the temperature dependence showed that rotaxane formation is enthalpically favored at the expense of a more

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Section: Complexation Of 8 With Diarylmagnesium Compoundsmentioning

confidence: 83%

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

et al. 2003

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“…Thus the tricyclic chloride 28 which has no hydrogens available for a 1,2-dehydrohalogenation undergoes instead a 1,4-elimination leading to [5]metacyclophane 91 :…”

Section: B 14-and Related Eliminationsmentioning

confidence: 99%

“…The isomeric 1,5-dehydroquadricyclane may be generated from the dihalides (91). The lithiation occurs at −78 • C but elimination and trapping only on warming to room temperature; trapping leads to two stereoisomeric [4 + 2]-adducts with DPIBF in 40% yield 208 .…”

Section: 2-and 13-eliminations In Quadricyclanesmentioning

confidence: 99%

Eliminations Involving Carbon–Halogen Bonds and Leading to Highly Strained Rings

Baird

Bolesov

2009

Patai's Chemistry of Functional Groups

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Dehydrohalogenations of Halogenated Cyclopropanes Elimination of Halogen 1,2‐Elimination of a Trialkylsilylhalide Eliminations Leading to Cyclopropa‐Aromatics 1,1‐ and 1,3‐Elimination Leading to Cyclopropenes 1,3‐Dehalogenation of 1‐Halo‐2‐Halomethylcyclopropanes Eliminations Leading to Bicyclo[1.1.0]but‐1(3)‐enes 1,2‐ and 1,3‐Eliminations in Quadricyclanes Dehalogenation and Dehydrohalogenation of Halogenated Cyclopropenes

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“…While [6] cyclophane (Scheme 1: 1, A = CH 2 CH 2 , X = H) is reasonably stable, 8 [5]metacyclophane (1, A = CH 2 , X = H) slowly polymerizes on standing at room temperature, 9 and [4]metacyclophane (1, A = -) is too unstable to be isolated, so that its intermediacy could only be demonstrated by interception reactions. 10 Correspondingly, the [n]paracyclophanes 2 (n = 8 or 7) are stable under ordinary conditions; [6]paracyclophane is a borderline case; [5]paracyclophane must be kept below À20°C;…”

Section: Reactions Of Small Cyclophanesmentioning

confidence: 99%

Unusual reactivity of highly strained cyclophanes

Bickelhaupt¹,

Wolf²

1998

J. Phys. Org. Chem.

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An essential feature of the concept of aromaticity has been the stability and lack of reactivity of aromatics relative to that of other unsaturated compounds. Contrary to this general experience, high and unusual reactivity is encountered when simple, monocyclic benzene rings are bent by short bridges into a boat-shaped conformation, as is the case in small [n] paracyclophanes (n 8) and [n]metacyclophanes (n 7). This is illustrated, mostly with examples taken from the authors' own work, for thermal and photochemical behavior and reactions with electrophiles, nucleophiles and dienophiles.

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[5]Metacyclophane

Cited by 46 publications

References 7 publications

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

Eliminations Involving Carbon–Halogen Bonds and Leading to Highly Strained Rings

Unusual reactivity of highly strained cyclophanes

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