Synthetically Useful Dipole-Stabilized Carbanions From Thioesters and Thiocarbamates

In an investigation of the formation of dipole-stabilized carbanions from thioesters, deprotonation of a tertiary center at the carbon adjacent to the sulfur of a thioester was found for the first time. Isopropyl, 2-octyl, and 4-tert-butylcyclohexyl 2,4,6-triisopropylthiobenzoates react with sec-butyllithium/TMEDA at -98(DEGREES)C to give synthetically useful (alpha)-lithio thioesters. These species react with electrophiles including primary alkyl halides and a variety of carbonyl compounds to give substituted thioesters. Study of the optically active 2-octyl thioester as well as the cis-4-tert-butylcyclohexyl thioester has shown that (alpha)-lithio thioesters are not configurationally stable. A general synthesis of trisubstituted thiiranes is provided by the action of sodium hydride on (beta)-hydroxy thioesters, which are obtained by reaction of the (alpha)-lithio thioesters with aldehydes.

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

• Becker, Peter Donald

• Chemistry, Organic

Identifier

(UMI)AAI8209543

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70179