Synthesis, structural characterization and photoisomerization of cyclic stilbenes

Oelgemöller, Michael; Frank, Ronald; Lemmen, Peter; Lenoir, Dieter; Lex, Johann; Inoue, Yoshihisa

doi:10.1016/j.tet.2012.03.038

Cited by 18 publications

(26 citation statements)

References 59 publications

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“…We have recently developed a new subclass of DAEs without the geometric constraint of the central endocyclic olefin bridge yet with two rings each involving one of the bridge’s carbon atoms to lock the photoreactive antiparallel conformation and thus provide stiff dithienylethenes (sDTEs), in analogy to stiff stilbenes [ 30 – 32 ]. Due to enabled isomerization of the central exocyclic double bond, sDTEs form a three-state system undergoing interconversion between ring-open E- and Z- isomers and a ring-closed C- isomer ( Scheme 1 ).…”

Section: Introductionmentioning

confidence: 99%

Oxidative and reductive cyclization in stiff dithienylethenes

Kleinwächter¹,

Teichmann²,

Grubert³

et al. 2018

Beilstein J. Org. Chem.

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The electrochemical behavior of stiff dithienylethenes, undergoing double bond isomerization in addition to ring-closure, has been investigated. Electrochromism was observed in almost all cases, with the major pathway being the oxidatively induced cyclization of the open isomers. The influence of the ring size (to lock the reactive antiparallel conformation) as well as substituents (to modulate the redox potential) on the electrocyclization was examined. In the series of derivatives with 6-membered rings, both the E- and the Z-isomer convert to the closed isomer, whereas for the 7-membered rings no cyclization from the E-isomer was observed. For both stiff and normal dithienylethenes bearing benzonitrile substituents an additional and rare reductive electrocyclization was observed. The mechanism underlying both observed electrocyclization pathways has been elucidated.

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Section: Introductionmentioning

confidence: 99%

Oxidative and reductive cyclization in stiff dithienylethenes

Kleinwächter¹,

Teichmann²,

Grubert³

et al. 2018

Beilstein J. Org. Chem.

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“…The diester 16 shows an undistorted geometry, with a torsional angle for E - 16 at 180.00(7)°, and for Z - 16 at 24.1(1)°, which is close to the values measured for unsubstituted stiff stilbenes ( i.e. , approximately 20°) [37].…”

Section: Resultsmentioning

confidence: 56%

“…Separation of E - 16 and enrichment of Z - 16 by recrystallization from ethanol, followed by chromatographic purification of Z - 16, afforded pure isomers. Photoisomerization of E - 16 was used to produce more of Z - 16 [37,38]. Hydrolysis with sodium hydroxide in ethanol afforded dicarboxylic acid Z - 17 (94% yield).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Properties of Bis-Porphyrin Molecular Tweezers: Effects of Spacer Flexibility on Binding and Supramolecular Chirogenesis

et al. 2015

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Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants K a = 10 4 -10 6 M´1 reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis.

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“…Solid state analysis and calculations were also reported by Oelgemöller et al. and are in agreement with the work described above …”

Section: Basic Propertiesmentioning

confidence: 99%

“…The 5‐membered fused ring analogue of stilbene (named stiff‐stilbene , Scheme b) was found to be much more stable, that is, clean photoisomerization occurs when exposed to UV light . This fused ring analogue has been used mostly as a prototype for investigating the photoisomerization path in stilbene as this process is simplified in this case due to steric restrictions.…”

Section: Introductionmentioning

confidence: 99%

Stiff‐Stilbene Photoswitches: From Fundamental Studies to Emergent Applications

Villarón

Wezenberg

2020

Angewandte Chemie

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Stiff‐stilbene, a sterically restricted fused ring analogue of stilbene, has been regularly used as a model compound in theoretical studies of stilbene photoisomerization. Lately, owing to its excellent photoswitching properties, it is increasingly being applied to reversibly control the properties and function of chemical as well as biological systems. Stiff‐stilbene photoswitches possess a number of advantageous properties including a high quantum yield for photoisomerization and a high thermal stability. Furthermore, they undergo a large geometrical change upon isomerization and their synthesis is straightforward. Herein, we provide an overview of the basic properties of stiff‐stilbene and of recent applications in supramolecular chemistry, catalysis, and biological systems.

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Synthesis, structural characterization and photoisomerization of cyclic stilbenes

Cited by 18 publications

References 59 publications

Oxidative and reductive cyclization in stiff dithienylethenes

Oxidative and reductive cyclization in stiff dithienylethenes

Synthesis and Properties of Bis-Porphyrin Molecular Tweezers: Effects of Spacer Flexibility on Binding and Supramolecular Chirogenesis

Stiff‐Stilbene Photoswitches: From Fundamental Studies to Emergent Applications

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