University of Illinois Urbana-Champaign

The Synthesis of (+/-)-Presilphiperfol-7(8)-Ene and Tertiary Tricyclo(5.3.1.0(4,11))undecanols Related to Presilphiperfolan-8-Ol

Duffy, Bryan C.

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Description

Title
The Synthesis of (+/-)-Presilphiperfol-7(8)-Ene and Tertiary Tricyclo(5.3.1.0(4,11))undecanols Related to Presilphiperfolan-8-Ol
Author(s)
Duffy, Bryan C.
Issue Date
1999
Doctoral Committee Chair(s)
Coates, Robert M.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
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.
Graduation Semester
1999
Type of Resource
text
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http://hdl.handle.net/2142/84434

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