Exploring the original proposed biosynthesis of (+)-symbioimine: remote exocyclic stereocontrol in a type I IMDA reaction.
The originally proposed biosynthesis of (+)-symbioimine was explored, resulting in the successful intramolecular Diels-Alder (IMDA) cyclization of an appropriate (E,E,E)-1,7,9-decatrien-3-one. In contrast to the originally proposed biosynthesis, the IMDA reaction appears to proceed via an endo transition state. Remarkably, a single exocyclic stereogenic center effectively controls the pi-facial selectivity affording a highly diastereoselective cycloaddition.
Burke
Jason P
JP
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
Sabat
Michal
M
Iovan
Diana A
DA
Myers
William H
WH
Chruma
Jason J
JJ
D000475:Alkenes / Q000737:chemistry; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis* / Q000737:chemistry* / Q000378:metabolism; D007659:Ketones / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
D000475:Alkenes; D006575:Heterocyclic Compounds, 3-Ring; D007659:Ketones; C505668:symbioimine