Abstract:Inversions in the periselectivity of formal aza-Diels–Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.
Steroidal 1-azadienes react with cyclic ketones to afford hexacyclic steroids via annulation reaction while the reaction with aldehydes gives pentacyclic steroids via hetero-Diels–Alder reactions.
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