| Abstract
| - The type 2 intramolecular N-acylazo Diels−Alder reaction provides a regio- and stereoselective synthesisof bicyclic 1,2-diazine systems. A new method for the generation of N-acylazo dienophiles with tetra-n-butylammonium periodate is reported. X-ray crystallographic analysis allowed the quantification ofstructural distortions of the nonplanar bridgehead olefin and lactam functionalities in 1,2-diazinecycloadducts 11 and 15. Caprolactams and enantholactams were formed by stereoselective bridgeheadalkene reduction, a process that transfers stereochemistry from the bridgehead lactam nitrogen to thebridgehead carbon. The sequence of transformations offers a convenient route for the diastereoselectivesynthesis of medium-ring nitrogen heterocycles and 1,4-diamines.
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