Oxidation of an allene compound bearing 1,8‐dichloroacridene moieties and photolysis of the halogenated allene compound for the generation of triplet carbenes

Fuku-en, Shin-ichi; Furukawa, Ko; Sasamori, Takahiro; Tokitoh, Norihiro; Abe, Manabu; Yamamoto, Yohsuke

doi:10.1002/poc.3398

Cited by 3 publications

(3 citation statements)

References 48 publications

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“…The Friedel‐Crafts alkylation of acridone itself yields 2,7‐di‐ tert ‐butylacrid‐9(10H)‐one . We became interested in an alternative approach using the directed lithiation of a diarylamine . We chose 4,4′‐di‐ tert ‐butyldiphenylamine because it is reasonably inexpensive, and the tert ‐butyl substituents would increase the solubility of the desired products.…”

Section: Resultsmentioning

confidence: 99%

Acridine Variations for Coordination Chemistry

Omolo

Bacsa

Sadighi

2020

Israel Journal of Chemistry

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This study describes the synthesis of an acridone through the directed lithiation of a diarylamine, and elaboration via the 4,5-dibromoacridone. The bromo substituents are amenable to Suzuki-Miyaura coupling. Conversion to a 9chloro-4,5-dibromoacridine, followed by bromine-lithium ex-change, allows the preparation of a 4,5-bis (phosphino)-9chloroacridine. The 9-chloro moiety undergoes nucleophilic aromatic substitution by methoxide or an aryloxide. Oneelectron reduction of a 9-(aryloxy)-4,5-bis(phosphino)acridine affords a stable radical anion.

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Section: Resultsmentioning

confidence: 99%

Acridine Variations for Coordination Chemistry

Omolo

Bacsa

Sadighi

2020

Israel Journal of Chemistry

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“…We designed a new strategy to generate triplet carbenes, based on 2‐electron oxidation of allenic precursors bearing heterocyclic moieties at their terminal positions (Scheme ) . Because this atomic arrangement does not change before and after oxidation, it is possible to introduce protecting groups X around the central carbon atom.…”

Section: Introductionmentioning

confidence: 97%

“…Because the system I bearing electron withdrawing Cl could not be easily oxidized (Fig. ), we introduced electron donating groups such as methoxy groups. However, oxidation of the allene compound bearing 1,8‐dimethoxyacridene moieties II did not give the desired triplet carbenes.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of allenes bearing 1,8‐diphenoxy or diaryloxyacridene moieties

Fuku-en

Yamamoto

Furukawa

et al. 2016

J of Physical Organic Chem

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New allene compounds bearing 1,8‐diphenoxy or bis(3,5‐di‐tert‐butylphenyl) oxyacridene (diaryloxyacridene) moieties were synthesized. These compounds were more easily oxidized than Cl‐substituted compounds. The allene compounds were oxidized to generate thermally stable triplet carbenes. Electron spin resonance and electron spin transient nutation spectra of the oxidation reaction products suggested the generation of triplet species; however, the main isolated product from the 1,8‐diphenoxy allene was a cyclized compound that was characterized by X‐ray analysis. The product derived from diaryloxy allene was also characterized by X‐ray analysis as a singlet species, which included a vinyl cation stabilized by a neighboring O(3,5‐di‐tert‐butylphenyl) group. This singlet species was stable even at room temperature and did not show any electron spin resonance signals in solution, indicating that the triplet species was not in equilibrium with the singlet. Copyright © 2016 John Wiley & Sons, Ltd.

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Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

Dolai

Kumar

Elvers

et al. 2022

Chemistry A European J

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Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC‐only and CAAC‐only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6] were investigated. The reduction of the conjugate acid of CAAC‐only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC‐only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon–carbon sigma bond formation. The resulting relatively elongated carbon–carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n‐dopants in organic semiconductor molecules.

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Oxidation of an allene compound bearing 1,8‐dichloroacridene moieties and photolysis of the halogenated allene compound for the generation of triplet carbenes

Cited by 3 publications

References 48 publications

Acridine Variations for Coordination Chemistry

Acridine Variations for Coordination Chemistry

Oxidation of allenes bearing 1,8‐diphenoxy or diaryloxyacridene moieties

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents

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