Highly Strained Cyclophanes

Tsuji, Takashi

doi:10.1002/3527603964.ch3

Cited by 10 publications

(4 citation statements)

References 10 publications

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“…This product could not be induced to rearrange to the structure 10 . A referee has pointed out that this result is not surprising since the structure may force the dihydrotriazine ring toward planarity thereby becoming approximately isosteric with the strained [4] meta cyclophane . However since there are six methylene groups linking the triazine C-3 to C-5 in structure 10 , the strain should be lessened as inferred by the Dreiding models, but it still could be significant.…”

Section: Resultsmentioning

confidence: 99%

One-Pot Synthesis of Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives from a Cascade Rearrangement Sequence in the Reactions of 1,2,3-Triazolium-1-aminide 1,3-Dipoles with Propiolate Esters

et al. 2006

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The reactions of 1,2,3-triazolium-1-aminides 1 (readily available from benzil bishydrazones) with propiolate esters leads to fluorescent 2,5-dihydro-1,2,3-triazine derivatives 2, 3 in one pot. These synthetic reactions can be carried out in acetone, in water, or under solvent-free conditions. The reactions involve a Huisgen cycloaddition followed by a sequence of rearrangements. The final ring-expansion step was blocked by linking a six-methylene hydrocarbon chain between the prospective 1,2,3-triazine C-4 and C-6 atoms, using substrate 8 which gave the fused tricyclic azapropellane product 9 exclusively. X-ray crystal structures were determined for two 2,5-dihydro-1,2,3-triazine derivatives and for compound 9. The UV absorption of the 1,2,3-triazine derivatives showed a dual absorption at ca. 310 and ca. 390 nm with fluorescent emission at ca. 480 and 528 nm (for excitation at 317 nm). The significant Stokes shift of ca. 200 nm shows the potential for biological fluorescent labeling experiments.

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Section: Resultsmentioning

confidence: 99%

One-Pot Synthesis of Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives from a Cascade Rearrangement Sequence in the Reactions of 1,2,3-Triazolium-1-aminide 1,3-Dipoles with Propiolate Esters

et al. 2006

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“…In cyclophanes, the π-electron subsystems are placed in close proximity and in a parallel arrangement. Therefore, an intense intramolecular electronic communication established by through-bond and through-space interactions is found . This overall theme has been exemplied for many arenes, heteroarenes, nonbenzoid π-systems, and even organometallic subunits.…”

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confidence: 94%

Phenothiazinophanes: Synthesis, Structure, and Intramolecular Electronic Communication

2008

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Ortho-phenylene, ethenylene, and ethylene-bridged phenothiazinophanes are synthesized by Suzuki coupling or McMurry dimerization and catalytic hydrogenation at ambient pressure. Intensive intramolecular electronic communication of the phenothiazinyl subunits is found according to cyclic voltammetry. In addition, the macrocycles display blue to green fluorescence with large Stokes shifts. In the solid state, the cyclophanes are arranged in unidimensional stacks. This orientation appears to be favorable for anisotropic charge transport in hole-transport materials for organic field effect transistors (OFET) applications.

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“…Aromatic systems which are distorted from planarity have long been objects of theoretical interest. Classic examples include paracyclophanes, peri-substituted acenes, helicenes, cyclacenes, bridged annulenes, and highly substituted porphyrins . The advent of fullerenes and carbon nanotubes has precipitated nothing short of a frenzy in the study of curved aromatics, and molecules such as corannulene and related polycycles which can be mapped onto the surface of fullenenes have consequently also enjoyed much attention .…”

Section: Introductionmentioning

confidence: 99%

Aromaticity and Curvature in Heteroacepentalenes

Mascal

2007

J. Org. Chem.

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Heteroatom-substituted acepentalene derivatives which are isoelectronic with the known acepentalenediide dianion are nonplanar, fused aromatic tricycles which are hemifullerenes of the corresponding C20 heteroanalogue. Depending on the number and position of heteroatoms, they may be anionic, neutral, or cationic. A nucleus-independent chemical shift study indicates that substitution of the central carbon of the acepentalenediide system with N or O results in a substantial increase in aromaticity. Peripheral aza substitution on the other hand tends to increase curvature and decrease aromaticity. Alkylation or protonation at the central position of asymmetrically substituted heteroacepentalenides leads to chiral, bowl-shaped, 10 pi aromatic species.

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Highly Strained Cyclophanes

Cited by 10 publications

References 10 publications

One-Pot Synthesis of Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives from a Cascade Rearrangement Sequence in the Reactions of 1,2,3-Triazolium-1-aminide 1,3-Dipoles with Propiolate Esters

One-Pot Synthesis of Fluorescent 2,5-Dihydro-1,2,3-triazine Derivatives from a Cascade Rearrangement Sequence in the Reactions of 1,2,3-Triazolium-1-aminide 1,3-Dipoles with Propiolate Esters

Phenothiazinophanes: Synthesis, Structure, and Intramolecular Electronic Communication

Aromaticity and Curvature in Heteroacepentalenes

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