Non-bonded interactions between proximate phenyl and polyfluorophenyl rings. Reactivity in polyfluoro[2.2]cyclophanes

Filler, Robert; Cantrell, Gary L.; Choe, E. W.

doi:10.1021/jo00380a006

Cited by 16 publications

(8 citation statements)

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“…Literature reports have shown that the insertion of fluorine atoms into one of the rings of 1 leads to a decrease in the reactivity of the nonsubstituted ring in Friedel−Crafts acylation reactions, which indicates that there is a transannular interaction capable of withdrawing electrons from the nonsubstituted ring . Additional tests gave evidence that 1 undergoes rearrangements under certain conditions (AlCl 3 /HCl), as opposed to 4 , which is inert . Attempts at acylating or brominating 4 also failed .…”

Section: Introductionmentioning

confidence: 99%

“…18 Additional tests gave evidence that 1 undergoes rearrangements under certain conditions (AlCl 3 /HCl), as opposed to 4, which is inert. 18 Attempts at acylating or brominating 4 also failed. 18 Experiments investigating hydrogen/deuterium exchange (DCl/AlCl 3 ) in 4 showed that only occasionally were all the hydrogen atoms exchanged for deuterium.…”

Section: Introductionmentioning

confidence: 99%

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A Computational Study of Tetrafluoro-[2.2]Cyclophanes

Caramori

Galembeck

2008

J. Phys. Chem. A

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A computational study of the isomers of tetrafluorinated [2.2]cyclophanes persubstituted in one ring, namely F4-[2.2]paracyclophane (4), F4-anti-[2.2]metacyclophane (5a), F4-syn-[2.2]metacyclophane (5b), and F4-[2.2]metaparacyclophane (6a and 6b), was carried out. The effects of fluorination on the geometries, relative energies, local and global aromaticity, and strain energies of the bridges and rings were investigated. An analysis of the electron density by B3PW91/6-31+G(d,p), B3LYP/6-31+G(d,p), and MP2/6-31+G(d,p) was carried out using the natural bond orbitals (NBO), natural steric analysis (NSA), and atoms in molecules (AIM) methods. The analysis of frontier molecular orbitals (MOs) was also employed. The results indicated that the molecular structure of [2.2]paracyclophane is the most affected by the fluorination. Isodesmic reactions showed that the fluorinated rings are more strained than the nonfluorinated ones. The NICS, HOMA, and PDI criteria evidenced that the fluorination affects the aromaticity of both the fluorinated and the nonfluorinated rings. The NBO and NSA analyses gave an indication that the fluorination increases not only the number of through-space interactions but also their magnitude. The AIM analysis suggested that the through-space interactions are restricted to the F4-[2.2]metacyclophanes. In addition, the atomic properties, computed over the atomic basins, gave evidence that not only the substitution, but also the position of the bridges could affect the atomic charges, the first atomic moments, and the atomic volumes.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Computational Study of Tetrafluoro-[2.2]Cyclophanes

Caramori

Galembeck

2008

J. Phys. Chem. A

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“…7b When exploiting this methodology using two different reactants, a statistical mixture of homo-and hetero-coupled products is expected. 10 However, in our particular case, only…”

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confidence: 70%

Synthesis of 1,2-biphenylethane based single-molecule diodes

et al. 2016

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We have described the synthesis of novel biphenylethane-based wires for molecular electronics. Exceptional single-molecule diode behavior was predicted for unsymmetrically substituted biphenylethane derivatives, synthesized here using the so far unexplored unsymmetrically substituted 1,2-bis(4-bromophenyl)ethanes as key intermediates, which were obtained from the corresponding tolane precursor by selective hydrogenation.

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“…They claimed that the proton pointing towards the fluorine (syn orientation) has a smaller chemical shift υ H ³ 2.7 than its anti counterpart υ H ³ 3.3 . Their assignment was not derived experimentally but by comparison with 4,5,7,8-tetrafluoro[2.2]paracyclophane (5), 6 in which the methylene groups adjacent to the fluorinated ring are shielded υ H D 2.98 relative to those next to the non-fluorinated ring υ H D 3.07 . The substituent effects derived by Huang et al 5 are the opposite of our own conclusion 2 and they also contradict the effects observed for a number of other ortho-substituents, including bromine 7 and chlorine.…”

Section: Introductionmentioning

confidence: 99%