Oxa-di-pi-methane photochemical rearrangement of quinuclidinones. Synthesis of pyrrolizidinones.
[reaction: see text] The oxa-di-pi-methane (ODPM) photochemical rearrangement, a triplet-sensitized sigmatropic 1,2-acyl shift of beta,gamma-enones, was successful utilizing methyl and heptyl 1-aza-3-carboalkoxybicyclo[2.2.2]oct-2-en-5-ones (quinuclidinones) as the photoprecursors. The cyclopropane of the heptyl ester tricyclic photoproduct could be opened with lithium dimethylcuprate or via hydrogenolysis to produce the corresponding pyrrolizidinone skeletons.
McClure
Cynthia K
CK
Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717, USA. cmcclure@chemistry.montana.edu
Kiessling
Anthony J
AJ
Link
Jeffrey S
JS