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The University of Southampton

Research project: Whitby: Insertion of carbenoids into zirconacycles

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A wide range of carbenoids insert into 5 member zirconacycle to give ring expanded species...

Scheme 1
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A wide range of carbenoids insert into 5 member zirconacycle to give ring expanded species – the first synthesis of zirconacyclohexanes and zirconacyclohexenes (scheme 1 ). [1]

Scheme 1. Formation of zirconacyclohexanes and zirconacyclohexenes.

Scheme 2
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The functionalised zirconacyclohexanes and zirconacyclohexenes have a rich chemistry with great potential for developing efficient multi component construction methods for organic compounds which we are just beginning to explore. Two examples of the type of tandem reaction sequencies we have developed are shown in scheme 2. In each case an unusual rearrangement leads to novel structure types.[2]

Scheme 2. Tandem reaction sequencies using zirconacycles.

Scheme 3
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For application to complex synthesis the regiochemistry of insertion of carbenoids needs to be predictable. We have established that insertions are almost always highly regioselective (Scheme 3)[3] but the reason for the contrasting regioselectivities observed is something we are still investigating by experimental and theoretical methods.

Scheme 3. Regioselectivity of insertion of carbenoids.

[1] Ring expansion of 5-to 6-member zirconacycles by carbenoid insertion, Dixon, S.; Fillery, S. M.; Kasatkin, A.; Norton, D.; Thomas, E.; Whitby, R. J. Tetrahedron 2004, 60, 1401-1416.

[2] A rearrangement to a zirconium-alkenylidene in the insertion of dihalocarbenoids and acetylides into zirconacycles, 1. Thomas, E.; Dixon, S.; Whitby, R. J. Angew. Chem. Int. Ed. 2006, 45, 7070-7072.

[3] The regiochemistry of zirconacycle elaboration, Thomas, E.; Dixon, S.; Whitby, R. J. Tetrahedron 2007, 63, 11686-11701. The regiochemistry of carbenoid insertion into zirconacycles, Gordon, G. J.; Luker, T.; Tuckett, M. W.; Whitby, R. J. Tetrahedron 2000, 56, 2113-2129.


Related research groups

Organic Chemistry: Synthesis, Catalysis and Flow
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