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The synthesis of 24-epicathasterone (20), 22-deoxy-24-epiteasterone (22) and 24-hydroxy-6-oxo-24-epicampestanol (24) via 22,23-epoxy- and 22,23-bromohydrin intermediates starting with ergosterol is reported. The structures of the new brassinosteroids were determined especially by X-ray analysis of intennediate bromohydrins.The synthesis of 24-epicathasterone, 22-deoxy-24-epiteasterone and 24-hydroxy-6-oxo-24-epicampestanol via 22,23-epoxy- and 22,23-bromohydrin intermediates starting with ergosterol is reported. The structures of the new brassinosteroids were determined especially by X-ray analysis of intermediate bromohydrins.