Persistent azulene α-carbocations: synthesis from aldehydes, spectroscopic and crystallographic properties

Catajina Harabajiu; Jodie L. Hann; Lloyd C. Murfin; Gabriele Kociok-Köhn; Simon E. Lewis

doi:10.1039/d2ob01695h

Persistent azulene α-carbocations: synthesis from aldehydes, spectroscopic and crystallographic properties

Catajina Harabajiu, Jodie L. Hann, Lloyd C. Murfin, Gabriele Kociok-Köhn, Simon E. Lewis

Material and Chemical Characterization Facility (MC2)

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Abstract

The non-benzenoid aromatic system azulene is sufficiently nucleophilic at C1 that it can react with a protonated aldehyde to form an α-azulenyl alcohol. This in turn may be protonated and undergo loss of water to give an azulene α-carbocation. We report the isolation of such azulenyl cations as salts with non-coordinating anions. The salts have been characterised by NMR, UV/Vis absorption and (in certain cases) X-ray crystallography. Reduction of representative salts to afford azulenyl(aryl) methylenes has been demonstrated.

Original language	English
Pages (from-to)	858-866
Number of pages	9
Journal	Organic and Biomolecular Chemistry
Volume	21
Issue number	4
Early online date	5 Jan 2023
DOIs	https://doi.org/10.1039/d2ob01695h
Publication status	Published - 5 Jan 2023

Bibliographical note

EPSRC - EP/R51164X/1

Funding

We thank EPSRC for IAA funding (EP/R51164X/1) and for DTG PhD studentships to L. C. M. and J. L. H. The authors acknowledge the Material and Chemical Characterisation Facility (MC2) at University of Bath (https://doi.org/10.15125/mx6j-3r54).

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/R51164X/1
University of Bath

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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AU - Kociok-Köhn, Gabriele

AU - Lewis, Simon E.

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Persistent azulene α-carbocations: synthesis from aldehydes, spectroscopic and crystallographic properties

Abstract

Bibliographical note

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