Tricarbonyliron(0) complexes of bio-derived η4 cyclohexadiene ligands: An approach to analogues of oseltamivir
Journal article, 2015

We have prepared novel [η4] and [η5]+ tricarbonyliron complexes from an unusual enantiopure cyclohexadiene ligand that possesses a quaternary stereocentre; this in turn is prepared through biotransformation of an aromatic ring. The cyclohexadiene ligand initially possessed two hydroxyl groups, both of which could be substituted with other functionality by means of an overall [η4] → [η5]+ → [η4] → [η5]+ → [η4] sequence. From six novel tricarbonyliron complexes which have been prepared, three have been characterised by x-ray crystallography. The reaction sequence we describe is potentially of relevance to the synthesis of analogues of the anti-influenza drug oseltamivir. In addition, the failure of an attempted addition of a bulky nitrogen nucleophile to an [η5]+ complex sheds light on the limits of reactivity for such additions. Thus, two bulky nucleophiles which are each known to add successfully to unencumbered [η5]+ complexes seemingly cannot be added sequentially to adjacent positions on the cyclohexadiene ligand.

Biotransformation

Arene cis-diol

Carbonyl

Davies-Green-Mingos rules

Influenza

Cyclohexadiene

Iron

Oseltamivir

Author

M. Ten Broeke

University of Bath

M. Ali Khan

University of Bath

G. Kociok-Köhn

University of Bath

Nina Kann

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry, Organic Chemistry

S. E. Lewis

University of Bath

Journal of Organometallic Chemistry

0022-328X (ISSN)

Vol. 799-800 19-29

Subject Categories

Organic Chemistry

DOI

10.1016/j.jorganchem.2015.09.005

More information

Latest update

2/21/2018