The synthesis of a series of bicyclo[4.2.2]octenones and bicyclo[3.2.2]heptenones by 1,3- or 1,2-migration reaction from 2-vinylbicyclo[2.2.2]octenols is reported. These ring-expansion reactions were accomplished under basic or neutral conditions. Whether 1,3- or 1,2-migration takes place depends on endo- or exocyclic olefin displacement in the substrates.
Bridged compounds Q 0060 1,3-and 1,2-Carbo-Migration of 2-Vinylbicyclo[2.2.2]octenols: Facile and Concise Synthesis of Bicyclo[4.2.2]/[3.2.2] Skeleton by Two/One-Carbon Ring Expansion. -The recently published anionic 1,3-carbo-migration [cf. (I→II) and (III→IV)], proceeds also by heating under neutral conditions [cf. (V→VI)]. Displacement of the endocyclic double bond by an exocyclic one leads to 1,2-migration products (VIII) under similar conditions. This migration protocols fail for substrates missing the cyclic ketal function.
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