title: Convergent stereocontrol in peterson olefinations. Application to the synthesis of (+/-)-3-hydroxybakuchiol and corylifolin.
abstract: The iron-catalyzed Kirmse reaction was used to generate neopentyl alpha-silyl thioethers that were elaborated to meroterpenes using two complementary routes: one route involved a sila-Pummerer rearrangement, and the other route involved a Peterson olefination. While severe eclipsing interactions undermined the efficiency of the stereospecific sila-Pummerer rearrangement, they made it possible to stereoselectively generate E olefins without isolation or separation of syn- and anti-beta-silyl alkoxides. Addition of a neopentyl alpha-silyl alkyllithium intermediate to an aryl aldehyde generated a mixture of syn- and anti-beta-silyl alkoxides. The syn-beta-silyl alkoxide eliminated stereospecifically at -78 degrees C to give an E olefin, whereas the anti-beta-silyl alkoxide was unreactive. The reaction mixture was then acidified and heated to induce stereospecific elimination of the anti isomer to give the same E olefin via a complementary cationic pathway. This route was used to complete the first synthesis of the meroterpene (+/-)-3-hydroxybakuchiol. In addition, we synthesized another meroterpene corresponding to the natural product corylifolin and offer evidence that the structure of corylifolin was misassigned.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
authors.forename: Joe B
authors.initials: JB
authors.lastname: Perales
authors.forename: Narubumi F
authors.initials: NF
authors.lastname: Makino
authors.forename: David L
authors.initials: DL
authors.lastname: Van Vranken