Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
Org Lett. 2010 Jul 16;12(14):3192-5. doi: 10.1021/ol101141a.
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.
原本提出的 (+)-symbioimine 的生物合成途径被探索，导致适当的 (E,E,E)-1,7,9-癸三烯-3-酮成功进行了分子内 Diels-Alder (IMDA) 环化反应。与原本提出的生物合成途径相反，IMDA 反应似乎通过内型过渡态进行。值得注意的是，单个非环立体中心有效地控制了 π-面选择性，从而提供了高度非对映选择性的环加成。
