Catalytic allylation of aldehydes mediated via the water-gas shift reaction

This dissertation details the progress made in the catalytic, nucleophilic allylation of aldehydes, as mediated through the action of the Water-Gas Shift reaction (WGSR). Through this work, three main objectives were sought. Firstly, an expansion of the scope of the allyl pro-nucleophile as a way to both improve the synthetic utility of the reaction and explore steric and electronic effects of the allyl pro-nucleophile on the course of the reaction. This effort resulted in the successful application of five different 2-subtituted allyl acetates and an additional two non-symmetrical allyl pro-nucleophiles across a range of aldehydes in good to excellent yield with high regioselectivity in the case of the non-symmetrical allyl sources. Furthermore, the highly chemoselective nature of the reaction was further revealed as both ketone and ester containing allyl sources were not shown to be subjected to an allylation reaction of the carbonyl. Next, an efficient means to render the allylation reaction enantioselective was sought through the addition of both free chiral ligand and pre-complexed metal catalysts. While successful in the generation of enantioenriched homoallylic alcohol products, synthetically viable er values were not able to be obtained using the current class of ligand backbones. Finally, several alternative methods were explored to enhance the utility of the WGS allylation reaction, including substitution of a more readily available metal catalyst and photochemical activation. Ultimately, each of these efforts did not result in a more efficient allylation reaction than the thermally activated ruthenium-catalyze reaction.

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

2017

Author dc:creator

• Matesich, Zachery D

Contributors dc:contributor

• Denmark, Scott E.
• Moore, Jeffery S.
• Rauchfuss, Thomas B.
• Burke, Martin D.

• Carbon monoxide
• Allylation
• Enantioselective
• Photochemical
• Organometallic

Statement dc:rights

• Copyright 2017 Zachery Matesich

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/98283

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/98283