The tricarbonyl(vinylketene)iron(o) complex 1 reacts with electron-poor alkenes to give decarbonylated adducts 3 and these are oxidised to tetrasubstituted cyclopropanes 4 using CAN; an X-ray crystal structure analysis of the adduct formed from 1 and dimethyl fumarate define its relative stereochemistry. But But3ad / 1 2a-d 4b-d a R1 = C02Me, R2 = H, R3 = C02Me; b R1 = H, R2 = C02Me, l? = C02Me; c R' = H, F? = COMe, R3 = C02Me; d R' = H, R2 = CF3, R3 = C02Et

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Alkynes add to (vinylketene)tricarbonyliron(O) complexes to generate stable adducts; addition of unsymmetrical alkynes is highly regioselective and the regiochemistries of the adducts produced in these reactions were determined by X-ray crystal structure analyses of the major isomer derived from but-3-yn-2-one and (3-tert-butyl-5-phenyl-I -0xapenta-I ,2,4-triene)tricarbonyIiron(O), and of the structurally modified product derived from diethylpropynylamine and (3-isopropyl-5-phenyl-I -0xapenta-I ,2-4-triene)tricarbonyIiron(O).

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