A Mild, Thermal Pentafulvene‐to‐Benzene Rearrangement

Finke, Aaron D.; Haberland, Sophie; Schweizer, W. Bernd; Chen, Peter; Diederich, François

doi:10.1002/anie.201304767

Cited by 17 publications

(11 citation statements)

References 27 publications

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“…The chemistry of tria-, penta-, and heptafulvenes − and fulvalenes ,,− (Figure A), their synthetic preparation, and the study of their physical properties have been the subject of continuous interest throughout the past decades. These nonalternant hydrocarbons do not exhibit classic Hückel aromaticity but can form ionic species upon reduction (pentafulvenes) or oxidation (tria- and heptafulvenes) that experience substantial aromatic stabilization via cyclic delocalization.…”

Section: Introductionmentioning

confidence: 99%

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

2018

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We describe the preparation of arylisocyanide monomers bearing conjugated fulvenyl groups derived from 9-benzylidene-9H-fluorene (Flu), 5-benzylidene-1,2,3,4-tetraphenylcyclopentadiene (TPCp), and 5-benzylidene-5H-dibenzo[a,d]cycloheptene (Dbs). The electrochemical and optical properties of the monomers and their precursors have been characterized and consistently showed the effect of the conjugation of the respective functional group (−NO2, −NH2, −NHCHO, and −NC) with the fulvenyl moiety. The isocyanides have been subsequently polymerized to the corresponding polyisocyanides (PICs), which exhibited number-average molecular weights of 124–136 kDa (PDI = 2.0–2.7), as determined by gel permeation chromatography in THF vs polystyrene standards. The thermal, optical, and electrochemical properties of the polymers have been studied in detail. Spectroelectrochemical analyses of polymers equipped with redox-active pentafulvene groups show reversible electrochromism, which allows to lower the optical gap from 2.38 to 1.20 eV (Flu) and from 2.27 to 1.55 eV (TPCp) via chemical or electrochemical reduction.

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Section: Introductionmentioning

confidence: 99%

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

2018

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“…In addition, the palladium-catalyzed [2 + 2 + 1] cycloaddition reaction of ( Z )- 3aa with diphenylacetylene could also proceed smoothly, affording a structurally intriguing pentasubstituted fulvene derivative 9 in 62% yield. 25 The structure of compound 9 was confirmed by X-ray crystallographic analysis. 26…”

Section: Resultsmentioning

confidence: 85%

Stereodivergent synthesis of β-iodoenol carbamates with CO₂viaphotocatalysis

Wang

Shi

et al. 2021

Chem. Sci.

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“…The synthesis of many DCFs is quite straightforward. Compounds 1 ,4a 3 ,4a 5 ,12 6 ,12 8 ,12 9 ,12 12 ,4b 13 ,4c 14 ,4c 15 ,12 16 ,13 17 ,14 18 ,4a and 20 12 were prepared as described previously. With the exception of compounds 3 , 12 , and 16 , the DCFs were prepared in one step from Knoevenagel condensation of the parent cyclopentadienones with malononitrile under Lehnert’s TiCl 4 /pyridine conditions,15 as previously described by Andrew et al 4a.…”

Section: Resultsmentioning

confidence: 99%

The 6,6‐Dicyanopentafulvene Core: A Template for the Design of Electron‐Acceptor Compounds

Finke

Jahn

Anas

et al. 2015

Chemistry A European J

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The electron-accepting ability of 6,6-dicyanopentafulvenes (DCFs) can be varied extensively through substitution on the five-membered ring. The reduction potentials for a set of 2,3,4,5-tetraphenyl-substituted DCFs, with varying substituents at the para-position of the phenyl rings, strongly correlate with their Hammett σp-parameters. By combining cyclic voltammetry with DFT calculations ((U)B3LYP/6-311+G(d)), using the conductor-like polarizable continuum model (CPCM) for implicit solvation, the absolute reduction potentials of a set of twenty DCFs were reproduced with a mean absolute deviation of 0.10 eV and a maximum deviation of 0.19 eV. Our experimentally investigated DCFs have reduction potentials within 3.67-4.41 eV, however, the computations reveal that DCFs with experimental reduction potentials as high as 5.3 eV could be achieved, higher than that of F4-TCNQ (5.02 eV). Thus, the DCF core is a template that allows variation in the reduction potentials by about 1.6 eV.

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A Mild, Thermal Pentafulvene‐to‐Benzene Rearrangement

Cited by 17 publications

References 27 publications

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

Stereodivergent synthesis of β-iodoenol carbamates with CO₂viaphotocatalysis

The 6,6‐Dicyanopentafulvene Core: A Template for the Design of Electron‐Acceptor Compounds

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A Mild, Thermal Pentafulvene‐to‐Benzene Rearrangement

Cited by 17 publications

References 27 publications

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

Stereodivergent synthesis of β-iodoenol carbamates with CO2viaphotocatalysis

The 6,6‐Dicyanopentafulvene Core: A Template for the Design of Electron‐Acceptor Compounds

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Stereodivergent synthesis of β-iodoenol carbamates with CO₂viaphotocatalysis