Pentacyclo[4.3.1.01,6.07,908,10]decane. A cyclopropane edge-bridged prismane and its rearrangement to a fulvene

Kostermans, G. B. M.; Hogenbirk, M.; Turkenburg, L. A. M.; Wolf, W. H. De; Bickelhaupt, F. Matthias

doi:10.1021/ja00243a066

Cited by 15 publications

(3 citation statements)

References 3 publications

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“…This reaction is evidently equal to the enterprise of converting the next lower homologue 15 into [4]metacyclophane (16), but the product is not stable as suggested by the isolation of its Dewar benzene valence isomer 17 (along with some other hydrocarbons). [19] The ability of the reaction to generate a benzene ring that would rather not be a benzene ring underscores its considerable power.…”

Section: Dehydrohalogenationmentioning

confidence: 99%

“…The first elimination is a normal dehydrohalogenation, but the second is extraordinary in that it occurs with concomitant opening of the three‐membered ring and enjoys the benefit of both strain relief and the formation of a new benzene ring. This reaction is evidently equal to the enterprise of converting the next lower homologue 15 into [4]metacyclophane ( 16 ), but the product is not stable as suggested by the isolation of its Dewar benzene valence isomer 17 (along with some other hydrocarbons) . The ability of the reaction to generate a benzene ring that would rather not be a benzene ring underscores its considerable power.…”

Section: Dehydrohalogenationmentioning

confidence: 99%

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Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

Bodwell

2014

The Chemical Record

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Note from the Editor: When we walk around a sculpture, it can speak to us in many ways, sometimes quite differently from various view points. Central to Tetsuo Nozoe and the Nozoe Autograph Book project are novel aromatic compounds. Just look at nearly any page and such compounds jump out at us. We can categorize them in many ways. Their structures. Their physical properties. Their pharmacological and toxicological properties. Their commercial utilities. Their symmetry. Their size. In this essay, Graham Bodwell brings to us his analysis of the various ways in which some of the most remarkable of these compounds have been ingeniously synthesized. We are privileged to have Bodwell's vision and his sense of organization and beauty. Tetsuo Nozoe would have beamed! —Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu

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Section: Dehydrohalogenationmentioning

confidence: 99%

Section: Dehydrohalogenationmentioning

confidence: 99%

Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

Bodwell

2014

The Chemical Record

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“…The system for n--4 with substituents is also known in its Dewar form [16,17]. The most interesting group is those for n = 5 and n = 6 since [6]paracyclophane (at least in the substituted form) occurs in both isomer forms, whereby the aromatic form is thermodynamically stable; there is indication that for [5]paracyclophanes the Dewar isomer is energetically the preferred species [10], at least in the substituted form.…”

Section: ~ ( Ch2) N~mentioning

confidence: 99%

Ab initio study of the stability of [n]paracyclophanes and their Dewar benzene-type isomers

Arnim

Peyerimhoff

1993

Theoret. Chim. Acta

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Summary. Ab initio calculations are carried out for [n]paracyclophanes andtheir Dewar benzene isomers for n = 5, 6, and 7 as well as for the benzene and Dewar benzene itself. The benzene isomers are studied b y employing various AO basis sets ranging from 6-31G type to such of triple-zeta type including two d and one f function on the carbons and two p and one d on the hydrogens. The correlation energy contribution is computed by employing MP2, CAS-SCF, MRD-CI and MCPF procedures. Potential curves for the low-energy states in the isomerization from benzene to its Dewar form are also computed under certain geometrical assumptions. The energy difference between the two potential minima is calculated to be 3.35 eV; neglect of electron correlation increases the value by about 0.3 eV, deficiencies in the polarization description (6-31G basis) overestimates it by another 0.65 eV. The calculations suggest that the experimental Dewar benzene geometry determination needs refinement and that the isomerization energy of hexamethylbenzene is considerably smaller than that of benzene itself.The geometries of the [n]paracyclophanes in both isomer forms are optimized in the 6-31G basis; the energy difference is determined by employing an AO basis of double-zeta quality plus polarization functions. Correlation effects are considered. The electronic isomerization energies are 2.58eV (n = 7), 1.63 eV (n = 6) and 0.7 eV (n = 5) for the unsubstituted compounds. The relative energetics are discussed in terms of potential surface diagram having the benzene ring deformation as the "reaction coordinate". Comparison with the anthracene isomerization is made and the effect of substituents is pointed out.

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Strained Aromatic Molecules

Smith

Liebman

Hopf

et al. 2009

Strained Hydrocarbons

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Pentacyclo[4.3.1.01,6.07,908,10]decane. A cyclopropane edge-bridged prismane and its rearrangement to a fulvene

Cited by 15 publications

References 3 publications

Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

Ab initio study of the stability of [n]paracyclophanes and their Dewar benzene-type isomers

Strained Aromatic Molecules

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