The reaction of 3β-tosyloxy-5α-cholesta-5,6β-diol with potassium t butoxide
in t-butanol has been further investigated.
5β-Hydroxy-4,5-secocholest-3-en-6-one was synthesised. It was shown
to undergo an ene reaction in decalin in a sealed tube at 200°C to give
primarily 3β-methyl-A-nor-5β-cholestan-5-o1 -6-one and 6β-hydroxy-4(5-6α)
abeo-cholestan-5-one. These primary products were further modified under
the reaction conditions to give 3-methyl-B-nor-5β-cholest-2-en-4-one and
The cyclohexane analogue, 3-methyl-3-(3-butenyl)-2-hydroxy-cyclohexanl-
one was synthesised. Heating under reflux in decalin gave 3β,7aβ-dimethyl-
4H-inden-4-one and an unidentified minor product.
The synthesis of 5-(2-propenyl)-5β-cholestan-2-ol-3-one was partially
The epimeric 5-(2-propenyl)-5β-cholestan-2-ol-3-one. was synthesised.
The ene reaction was observed in refluxing toluene giving 2α,5-(1-methylethano)-5α-cholestan-2β-ol-3-one and 3α,5-(methyethano)-5α-cholestan-3β–ol-2-one.
The ketone analogue, 5-(2-propenyl )-5α-cholestan-3-one underwent an
ene reaction in decalin in a sealed tube at 250°C to give 2α,5-(1-methylethano)
A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.