Valuable new cyclohexadiene building blocks from cationic η5-iron-carbonyl complexes derived from a microbial arene oxidation product

Monika Ali Khan, Mary F. Mahon, John P. Lowe, Alan J. W. Stewart, Simon E. Lewis

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Biooxidation of benzoic acid by Ralstonia eutropha B9 provides an unusual cyclohexadiene carboxy diol that contains a quaternary stereocentre. Tricarbonyliron derivatives of this chiron, on treatment with acid, give two isomeric η5-cyclohexadienyl complexes as observed by NMR spectroscopy. Both of these can be subjected to the addition of nucleophiles to provide isomeric cyclohexadiene complexes with new substituent patterns, several of which have been characterised crystallographically. De-metallation of these provides a versatile library of cyclohexadiene building blocks, the utility of which is demonstrated by formal syntheses of oseltamivir. The mechanism of product formation and its stereochemical implications are discussed, as are the procedures undertaken to establish the enantiopurity of a representative cyclohexadiene product.
Original languageEnglish
Pages (from-to)13480-13493
JournalChemistry - A European Journal
Volume18
Issue number42
DOIs
Publication statusPublished - 15 Oct 2012

Fingerprint

Iron
Oxidation
Oseltamivir
Nucleophiles
Benzoic Acid
Nuclear magnetic resonance spectroscopy
Derivatives
Acids
1,4-cyclohexadiene

Cite this

Valuable new cyclohexadiene building blocks from cationic η5-iron-carbonyl complexes derived from a microbial arene oxidation product. / Ali Khan, Monika; Mahon, Mary F.; Lowe, John P.; Stewart, Alan J. W.; Lewis, Simon E.

In: Chemistry - A European Journal, Vol. 18, No. 42, 15.10.2012, p. 13480-13493.

Research output: Contribution to journalArticle

@article{4231e8ab3dd1421cbdc0984050dc3d9f,
title = "Valuable new cyclohexadiene building blocks from cationic η5-iron-carbonyl complexes derived from a microbial arene oxidation product",
abstract = "Biooxidation of benzoic acid by Ralstonia eutropha B9 provides an unusual cyclohexadiene carboxy diol that contains a quaternary stereocentre. Tricarbonyliron derivatives of this chiron, on treatment with acid, give two isomeric η5-cyclohexadienyl complexes as observed by NMR spectroscopy. Both of these can be subjected to the addition of nucleophiles to provide isomeric cyclohexadiene complexes with new substituent patterns, several of which have been characterised crystallographically. De-metallation of these provides a versatile library of cyclohexadiene building blocks, the utility of which is demonstrated by formal syntheses of oseltamivir. The mechanism of product formation and its stereochemical implications are discussed, as are the procedures undertaken to establish the enantiopurity of a representative cyclohexadiene product.",
author = "{Ali Khan}, Monika and Mahon, {Mary F.} and Lowe, {John P.} and Stewart, {Alan J. W.} and Lewis, {Simon E.}",
year = "2012",
month = "10",
day = "15",
doi = "10.1002/chem.201202411",
language = "English",
volume = "18",
pages = "13480--13493",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-Blackwell",
number = "42",

}

TY - JOUR

T1 - Valuable new cyclohexadiene building blocks from cationic η5-iron-carbonyl complexes derived from a microbial arene oxidation product

AU - Ali Khan, Monika

AU - Mahon, Mary F.

AU - Lowe, John P.

AU - Stewart, Alan J. W.

AU - Lewis, Simon E.

PY - 2012/10/15

Y1 - 2012/10/15

N2 - Biooxidation of benzoic acid by Ralstonia eutropha B9 provides an unusual cyclohexadiene carboxy diol that contains a quaternary stereocentre. Tricarbonyliron derivatives of this chiron, on treatment with acid, give two isomeric η5-cyclohexadienyl complexes as observed by NMR spectroscopy. Both of these can be subjected to the addition of nucleophiles to provide isomeric cyclohexadiene complexes with new substituent patterns, several of which have been characterised crystallographically. De-metallation of these provides a versatile library of cyclohexadiene building blocks, the utility of which is demonstrated by formal syntheses of oseltamivir. The mechanism of product formation and its stereochemical implications are discussed, as are the procedures undertaken to establish the enantiopurity of a representative cyclohexadiene product.

AB - Biooxidation of benzoic acid by Ralstonia eutropha B9 provides an unusual cyclohexadiene carboxy diol that contains a quaternary stereocentre. Tricarbonyliron derivatives of this chiron, on treatment with acid, give two isomeric η5-cyclohexadienyl complexes as observed by NMR spectroscopy. Both of these can be subjected to the addition of nucleophiles to provide isomeric cyclohexadiene complexes with new substituent patterns, several of which have been characterised crystallographically. De-metallation of these provides a versatile library of cyclohexadiene building blocks, the utility of which is demonstrated by formal syntheses of oseltamivir. The mechanism of product formation and its stereochemical implications are discussed, as are the procedures undertaken to establish the enantiopurity of a representative cyclohexadiene product.

UR - http://www.scopus.com/inward/record.url?scp=84867200214&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1002/chem.201202411

U2 - 10.1002/chem.201202411

DO - 10.1002/chem.201202411

M3 - Article

VL - 18

SP - 13480

EP - 13493

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 42

ER -