The Stetter reaction : synthesis of complex spiro Bis-indanes and studies on quaternary centre formation

This work covers recent advances in the Stetter reaction, including two novel domino Stetter reactions and preliminary studies on quaternary center formation via the intermolecular Stetter reaction. The N-heterocyclic carbene (NHC) catalyzed domino Stetter-aldol-Michael dimerization of o-formyl chalcone derivatives 36 affords spiro bis-indane homo-dimers 38 in good yields and moderate to high diastereomeric ratios. Three carbon-carbon bonds, including the hindered quaternary center at the spiro ring junction, form at a remarkable rate under mild reaction conditions. Spiro bis-indanes 39 are also produced in moderate to good yields through the Stetter-aldol-aldol reactions of o-formyl chalcones 36 with phthalaldehyde derivatives 27. The scope, limitations, and potential applications of these remarkable complexity-generating domino reactions are discussed. Preliminary results in the formation of quaternary centers via the intermolecular Stetter reaction are also disclosed. The viability of β,β-disubstitued Meldrum’s acid, diethyl malonate, and malononitrile alkylidenes as well as diphenylcyclopropenone and 3-phenylcyclobutenone as acceptors in the Stetter reaction are discussed.

Name thesis:degree_name

Master of Science (M.Sc.)

Level thesis:degree_level

Masters

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Saskatchewan

Year dc:date.issued

2013

Author dc:creator

• Holmes, Janice

Advisor dc:contributor.advisor

• Gravel, Michel

Committee members dc:contributor.committeemember

• Krol, Ed S.
• Majewski, Marek
• Dimmock, Jonathan R.

• Stetter reaction
• carbenes
• organocatalysis
• umpolung
• domino reactions

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/10388/ETD-2012-09-523

OAI identifier oai:identifier

oai:harvest.usask.ca:10388/ETD-2012-09-523