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Postgraduate Training:
Cancer Medicinal Chemistry:
4 year programme funded by CRUK
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Asymmetric Synthesis
The natural product targets which we have tackled in the Hulme group have required us to develop new synthetic methodology and to push the limits of methodology which has been introduced by others.
Thiol Chiral auxiliary
We have shown that thioesters are easily displaced by nucleophiles such as the phosphonate anion (Synlett, 1998) and so we have recently developed a new thiol analogue of the Masamune auxiliary (Org. Lett., 2006). This shows high selectivity in anti aldol reactions with a range of aldehydes (dr 91:9-97:3) and may be easily displaced by a range of nucleophiles.
Evans Tishchenko reaction
We have been the first to show that the Evans-Tishchenko reaction can be used on enones (Tetrahedron Lett., 1997) and with complex polyfunctional aldehyde substrates. Developing this methodology was critical to our recent success in the synthesis of the carbon skeleton of octalactin A (Org. Lett., 2007) where we used an Evans-Tishchenko reaction to join two key fragments with subsequent RCM closure of the eight-membered ring.
Aldol reactions with Alpha Amino Aldehdyes
We have investigated the glycolate aldol reactions of complex alpha amino aldehydes to generate both "matched" (Perkin Trans. 1, 2000) and "mismatched" (Org. Lett., 2002) aldol adducts. We have applied this methodology to the synthesis of the iminosugars DAB-1 and nectrisine, and to the synthesis of the protein synthesis inhibitor anisomycin.
