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The University of Southampton
Chemistry

Research project: Whitby: Natural product synthesis using zirconium chemistry

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Natural products provide excellent targets for illustrating and challenging the organometallic chemistry we have developed.

Cocyclisation of unactivated alkenes and/or alkynes to give a zirconacycle provides a novel C-C bond forming method often with excellent diastereocontrol.

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Simple protonation has been used to synthesise natural products such as galbulin (1) [1] whereas carbonylation provided a short route to tecomanine (2 ) [2] (a potent hypoglycaemic agent isolated from leaves used in Mexico to treat diabetes).

 

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Insertion of allyl carbenoids followed by aldehydes provides an excellent convergent access to many terpenoid structures, for example the ‘two pot' synthesis of 9-hydroxysargaquinone 3.[3] A more complex example is the total synthesis of the dollabellane diterpene acetoxyodontoschismenol (4) where zirconium chemistry is used to assemble all the carbons needed for the skeleton from three components in one step.[4]

 

[1] Short total synthesis of (±)-galbulin and (±)-isogalbulin using zirconium chemistry Kasatkin, A. N.; Checksfield, G.; Whitby, R. J. J. Org. Chem. 2000, 65, 3236-3238.

[2] A Zirconium Mediated Synthesis of (±)-Tecomanine Kemp, M. I.; Whitby, R. J.; Coote, S. J. Synthesis 1998, 557-568.

[3] Zirconium mediated total synthesis of crinitol, 9-hydroxyfarnesoic acid, 9-hydroxyfarnesol, 9-hydroxysargaquinone and the selectively-protected aglycone of moritoside and euplexide A, Dixon, S.; Gordon, G. J.; Whitby, R. J. Chem. Commun. 2005, 4303-4305.

[4] Total synthesis of (+/-)-acetoxyodontoschismenol using zirconium chemistry, Baldwin, I. R.; Whitby, R. J. Chem. Commun. 2003, 2786-2787.

Related research groups

Organic Chemistry: Synthesis, Catalysis and Flow
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