Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold

Petter Dunås; Lloyd C. Murfin; Oscar J. Nilsson; Nicolas Jame; Simon E. Lewis; Nina Kann

doi:10.1021/acs.joc.0c01412

Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold

Petter Dunås, Lloyd C. Murfin, Oscar J. Nilsson, Nicolas Jame, Simon E. Lewis, Nina Kann

Department of Chemistry

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Abstract

The functionalization of azulenes via reaction with cationic η⁵-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43−98% yield. The products were examined with UV− vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle.

Original language	English
Pages (from-to)	13453-13465
Number of pages	13
Journal	Journal of Organic Chemistry
Volume	85
Issue number	21
Early online date	21 Oct 2020
DOIs	https://doi.org/10.1021/acs.joc.0c01412
Publication status	Published - 6 Nov 2020

Funding

The Swedish Research Council (N.K., grant 2015-05360), the Swedish Research Council Formas (N.K., grant 2015-1106), and the Engineering and Physical Sciences Research Council (S.E.L., grant EP/L016354/1) are gratefully acknowledged for funding. We thank Dr. Andrew Paterson, Chemspeed Technologies, for his discussions and Jennifer Tamayo Núñez for her assistance in preparing one of the azulenes.

ASJC Scopus subject areas

Organic Chemistry

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10.1021/acs.joc.0c01412Licence: CC BY

___JOC_2020_85_13453___Final published version, 2.36 MBLicence: CC BY

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title = "Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold",

abstract = "The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43−98% yield. The products were examined with UV− vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle.",

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doi = "10.1021/acs.joc.0c01412",

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AU - Dunås, Petter

AU - Murfin, Lloyd C.

AU - Nilsson, Oscar J.

AU - Jame, Nicolas

AU - Lewis, Simon E.

AU - Kann, Nina

PY - 2020/11/6

Y1 - 2020/11/6

N2 - The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43−98% yield. The products were examined with UV− vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle.

AB - The functionalization of azulenes via reaction with cationic η5-iron carbonyl diene complexes under mild reaction conditions is demonstrated. A range of azulenes, including derivatives of naturally occurring guaiazulene, were investigated in reactions with three electrophilic iron complexes of varying electronic properties, affording the desired coupling products in 43−98% yield. The products were examined with UV− vis/fluorescence spectroscopy and showed interesting halochromic properties. Decomplexation and further derivatization of the products provide access to several different classes of 1-substituted azulenes, including a conjugated ketone and a fused tetracycle.

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 21

ER -

Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold

Abstract

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Azulene functionalization by iron-mediated addition to a cyclohexadiene scaffold

Abstract

Funding

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MC2- X-ray diffraction (XRD)

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