Asymmetric α-Alkylation of Acyclic Ketones Utilizing Chiral Nonracemic N-Amino Cyclic Carbamate Hydrazones

Asymmetric variants of ketone α-alkylation are highly important given that numerous natural products, drugs, and related compounds exist as α-functionalized ketone or derivatives thereof. A method for asymmetric α-alkylation of ketones using N-Amino cyclic carbamate (ACC) chiral auxiliaries is described. ACC alkylation delivers excellent stereoselectivity and yields, with a camphor-derived ACC auxiliary exhibits the highest stereoselectivities. A full account of this ACC method is discussed herein, including the synthesis of camphor-derived ACC auxiliaries, an amination method for preparation of ACC auxiliaries from commercially available oxazolidinones, and the study of the regioselectivity and diastereoselectivity of ACC hydrazone alkylation to determine factors compromising the selectivities.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Doctoral

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Houston

Year dc:date.issued

2017

Author dc:creator

• Huynh, Uyen 1986-

Advisor dc:contributor.advisor

• Coltart, Don M.

Committee members dc:contributor.committeemember

• May, Jeremy A.
• Miljanić, Ognjen Š.
• Teets, Thomas S.
• Bornmann, William G.

• ACC auxiliary
• Ketone alpha alkylation
• Azaenolate
• Enantioselective
• Asymmetric
• Carbon–carbon bond formation
• Amination
• Monochloramine

Statement dc:rights

• The author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/10657/2870

OAI identifier oai:identifier

oai:uh-ir.tdl.org:10657/2870