Type 2 intramolecular N-acylnitroso Diels-Alder reaction: scope and application to the synthesis of medium ring lactams.
Heteroatom variants of the type 2 intramolecular Diels-Alder reaction provide an efficient method for the preparation of bridged bicyclic heterocycles. The type 2 variant of the intramolecular N-acylnitroso Diels-Alder reaction is an effective method for the synthesis of bridged bicyclic oxazinolactams. Structural studies of the cycloadducts have allowed for quantification of the deformations of the bridgehead functionalities and provided a strategy for the stereoselective synthesis of substituted seven- and eight-membered ring lactams. Diastereoselective cycloadditions followed by cleavage of the oxazine ring afford azepin-2-ones or azocin-2-ones.
Sparks
Steven M
SM
Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
Chow
Chun P
CP
Zhu
Liang
L
Shea
Kenneth J
KJ
D000215:Acylation; D001381:Azepines / Q000737:chemistry; D001392:Azocines / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D003500:Cyclization; D006865:Hydrogenation; D007769:Lactams / Q000138:chemical synthesis*; D015394:Molecular Structure; D009603:Nitroso Compounds / Q000737:chemistry*; D010078:Oxazines / Q000737:chemistry; D013237:Stereoisomerism
D001381:Azepines; D001392:Azocines; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007769:Lactams; D009603:Nitroso Compounds; D010078:Oxazines