Use of the Cyclopropylcarbinyl - Allylcarbinyl Rearrangement as a Probe of the Thiophilic Addition Reaction Mechanism

The mechanism of thiophilic addition was examined using the reported ring opening rearrangements of cyclopropylcarbinyl species as a probe to determine whether the reaction proceeds in a one or two electron fashion. A number of alpha-cyclopropyl thioketones were examined for their suitability as probes. These investigations were hampered by generally low thiophilic yields and the failure of the substrates examined to undergo ring openings independently characterizable as anionic or radical anionic as required for the successful diagnostic use of the cyclopropylcarbinyl-allylcarbinyl rearrangement. Cyclic voltammetry was examined as a technique to generate and characterize electrochemically the chemistry of the thioketyl radical anion of 1. These experiments indicated that 1 underwent an irreversible one electron reduction and permitted us to set the upper limit on the lifetime of this radical anion at <10('-2) sec at ambient temperatures. Evidence gathered from the reactions of 1 with organolithiums was presented which was consistent with a two electron thiophilic addition mechanism. Attempts to independently generate and unambiguously characterize the intermediates from 1 proposed to lie on the two electron and one electron reaction paths were unsuccessful.

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

• Garrett, Curtis Gene

• Chemistry, Organic

Identifier

(UMI)AAI8521768

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70298