Blitzvakuumthermolyse von 1‐Chlor‐4‐methylen‐spiro[2.m]alkanen

Jenneskens, Leonardus W.; Wolf, W. H. De; Bickelhaupt, F.

doi:10.1002/cber.19861190234

Cited by 4 publications

(2 citation statements)

References 11 publications

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“…The mixture turned green, then brownish, and finally black. It was stirred for 0.5 h at room temp., and the resulting black suspension was transferred to a dropping funnel (under nitrogen) and slowly added to a cooled mixture of CFCl 3 (22.5 mmol, 3.08 g) and 9,9-dichlorobicyclo[5.3.0]dec-1(7)-ene (2, Y ϭ Cl) [31] (5 mmol, 1.02 g) in dry THF (40 mL) whilst stirring at such a rate that the temperature did not exceed 0°C.…”

Section: -Chloro-11-fluoro[5]metacyclophane (1e)mentioning

confidence: 99%

Unusual Reactions of Halo[5]metacyclophanes

Wijsman¹,

Boesveld²,

Goedheijt³

et al. 2002

Eur. J. Org. Chem.

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The synthesis of novel [5]metacyclophanes 1 has been achieved either by an improved version of the general approach starting from halobicyclo[5.3.0]dec-1(7)-enes 2 or by nucleophilic substitution of 11-chloro[5]metacyclophanes. Conformational analysis of 1 revealed that the exo conformation, in which the pentamethylene bridge is pointing away from the aromatic ring, is strongly preferred both for very small and for very large substituents at the aromatic interbridge position 11, whereas medium-sized substituents induce the occurrence of minor amounts of the endo conformer. In Diels−Alder reactions with dienophiles, compounds 1 behaved like reactive dienes, adding at positions 8 and 11 of the aromatic ring. Substitution by chlorine, though, reduced the reaction rate; the unsymmetrical dienophile acrylonitrile showed little preference for the two possible regioisomeric adducts 8 and 9. Similarly, compounds 1 were unusually reactive towards acid, and interesting and unforeseen rearrangements were observed. Depending on the substituent at position 11, acid treatment of 1 afforded either ortho-annu-

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Section: -Chloro-11-fluoro[5]metacyclophane (1e)mentioning

confidence: 99%

Unusual Reactions of Halo[5]metacyclophanes

Wijsman¹,

Boesveld²,

Goedheijt³

et al. 2002

Eur. J. Org. Chem.

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“…The synthetic utility of the conjugated triene products is evident . For example, triene 14 smoothly reacted with the dienophile, tetracyanoethylene, within a few minutes at 25 °C to afford Diels−Alder adducts with good selectivity (Scheme ) .…”

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confidence: 99%

Conjugated Enynes as a New Type of Substrates for Olefin Metathesis

Kang

Kim

et al. 2003

Org. Lett.

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[reaction: see text] It has been demonstrated for the first time that conjugated enynes can be employed as a facile substrate in olefin metathesis with the use of a bispyridine-substituted ruthenium benzylidene catalyst. Cross-metathesis of the enynes with alkenes turns out to proceed with preferential formation of (Z)-isomers over (E)-isomers up to >25:1 in moderate to good yields. The intramolecular version of conjugated enynes affords novel butadienyl cycloalkenes, which are a highly useful synthetic building blocks, in acceptable yields.

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