The Synthesis of (+/-)-Presilphiperfol-7(8)-Ene and Tertiary Tricyclo(5.3.1.0(4,11))undecanols Related to Presilphiperfolan-8-Ol
type: CreativeWork
description: Functionalization reactions of the double bond of 15-nor-PSP-7(8)-ene were carried out to investigate the possible synthesis of (+/-)-PSP-8-OH from (+/-)-PSP-7(8)-ene. Epoxidation of the double bond with an aqueous buffered m-chloroperbenzoic acid furnished a 2.5:1 mixture of the 7beta,8beta- and 7beta,8beta-epoxides. m-Chlorobenzoic acid catalyzed a facile rearrangement of the 7beta,8beta-epoxide to 15- nor-cameroon-7-one was investigated. Reaction of nor-PSP-7(8)-ene with osmium tetroxide afforded nor-presilphiperfolan-7a,8a-diol, which underwent pinacol rearrangement to 8,10,10-trimethyltricyclo[6.2.1.01,5]undecan-11-one. The same ketone was formed directly by reaction of nor-PSP-7(8)-ene with chromyl chloride. The mechanistic pathways and stereochemical implications of these rearrangements are discussed in detail.
abstract: Functionalization reactions of the double bond of 15-nor-PSP-7(8)-ene were carried out to investigate the possible synthesis of (+/-)-PSP-8-OH from (+/-)-PSP-7(8)-ene. Epoxidation of the double bond with an aqueous buffered m-chloroperbenzoic acid furnished a 2.5:1 mixture of the 7beta,8beta- and 7beta,8beta-epoxides. m-Chlorobenzoic acid catalyzed a facile rearrangement of the 7beta,8beta-epoxide to 15- nor-cameroon-7-one was investigated. Reaction of nor-PSP-7(8)-ene with osmium tetroxide afforded nor-presilphiperfolan-7a,8a-diol, which underwent pinacol rearrangement to 8,10,10-trimethyltricyclo[6.2.1.01,5]undecan-11-one. The same ketone was formed directly by reaction of nor-PSP-7(8)-ene with chromyl chloride. The mechanistic pathways and stereochemical implications of these rearrangements are discussed in detail.
author: Duffy, Bryan C.
language: eng
keywords: Chemistry, Organic
date published: 2015-09-25T22:14:29Z
date modified: 2026-07-22T22:26:23Z
provider: University of Illinois - Urbana-Champaign
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Illinois at Urbana-Champaign

PropertyValue
property ID: Handle
value: http://hdl.handle.net/2142/84434