Development of a catalytic enantioselective intramolecular Stetter reaction: catalyst development and synthetic applications

A triazolinylidene carbene-catalyzed enantioselective intramolecular Stetter reaction has been developed. The process involves direct conversion of an aldehyde into a chiral acyl anion equivalent and its addition into a pendant electron-deficient olefin. The development of chiral bicyclic nucleophilic carbene catalysts has allowed for increased efficiency and selectivity in this reaction, as well as an overall broadening of its synthetic utility. The highly stereoselective formation of five- and six-membered rings has been realized in this reaction manifold. Extensive catalyst development has identified a number of catalysts which often provide complementary reactivity and selectivity. Aliphatic and aromatic aldehydes both participate in the addition to a variety of Michael acceptors. Synthetically important enantioenriched 1,4-dicarbonyl compounds can be generated in a single operation from achiral materials. The Stetter reaction has been developed to construct challenging quaternary stereocenters with good efficiency and very high selectivity. The scope of this transformation is quite broad, and holds significant promise for further reaction development. Synthetic applications have been investigated in the arena of natural product synthesis. Progress has been made utilizing the Stetter reaction for a key bond construction in an effort to enantioselectively synthesize a complex alkaloid. The key Stetter reaction in this system affords the desired product in good yield and excellent enantioselectivity.

Name thesis:degree_name

Doctor of Philosophy (Ph.D.)

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor dc:publisher

Colorado State University. Libraries

Year dc:date.issued

2007

Authors dc:creator

• Kerr, Mark Steven, author
• Rovis, Tomislav, advisor
• Anderson, Oren P., committee member
• Bernstein, Elliot R., committee member
• McNeil, Michael, committee member
• Williams, Robert M., committee member

• organic chemistry

Statement dc:rights

• Copyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.

Language dc:language.iso

eng, English

Identifier URI

https://doi.org/10.25675/3.026524

OAI identifier oai:identifier

oai:mountainscholar.org:10217/243837