Silver salts Cope rearrangement

This reaction exhibits strong analogy with the silver-promoted cationic aza-Cope rearrangement described by Overman et al. As a new route toward alkaloids, these authors showed thatcyanomethylamines carrying unsaturated chain led to pyrrolidine or piperidine derivatives on treatment with silver salts depending on the substituent (Scheme 3.38) 59 60... 

The power of pericyclic reactions for forming new carbon-carbon bonds is nicely illustrated by the use of the Claisen orthoester rearrangement to prepare y-ketoesters with a quaternary centre next to the ketone (Scheme 9)The use of silver salts to catalyse the acetylenic oxy- Cope rearrangement for the preparation of a,0-6,e-unsaturated ketones has also been reported [equation (10)].57... 

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