Studies of the Synthesis of Polycyclic Homocyclopropylcarbinols

A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metallated cyclopropane ring onto the epoxide. A series of bromocyclopropyl epoxides was prepared from diene precursors in three or four steps by dibromocyclopropanation, epoxidation, and stereoselective reduction of one bromine atom. As an example, endo-7-bromobicyclo{4.1.0}hept-3-ene anti-oxide prepared from 1,4-cyclohexadiene underwent cyclization to endo-tricyclo{3.2.0.0('2,7)}-heptan-4-ol in 69% yield. Lithiation of a stereoisomeric mixture of the bromocyclopropyl epoxides from 1,5-hexadiene afforded the endo and exo isomers of both bicyclo{4.1.0}heptan-3-ol and bicyclo{3.1.0}hexane-2-methanol.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Last, Larry Alan

• Chemistry, Organic

Identifier

(UMI)AAI8422113

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70254