Trichothecene Analogues. Total Synthesis of 12,13-Epoxy-14-methoxytrichothecene via Organoiron Complexes

Article abstract of DOI:10.1021/ja00412a025

The use of tricarbonyl(4-methoxy-1-methylhexadienylium)iron hexafluorophosphate (4) as a ring A precursor for 12,13-epoxytrichothecene synthesis is described.Reaction of 4 with methyl 2-oxo-1-potassiocyclopentanecarboxylate gave the diastereomeric complexes 5 and 6, in quantitative yield.Both these isomers were converted to olefin 15, followed by stereospecific epoxidation to give 16 which was converted to the cyclohexanone 18.Regio- and stereocontrolled hydrolytic epoxide opening with concominant Michael cyclization gave the bisnortrichothecane 19 which was converted in five steps to the title trichothecene analogue 25.