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

Matesich, Zachery D

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https://hdl.handle.net/2142/98283 Copy

Description

Title

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

Author(s)

Matesich, Zachery D

Issue Date

2017-07-13

Director of Research (if dissertation) or Advisor (if thesis)

Denmark, Scott E.

Doctoral Committee Chair(s)

Denmark, Scott E.

Committee Member(s)

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

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Carbon monoxide
• Allylation
• Enantioselective
• Photochemical
• Organometallic

Abstract

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.

Graduation Semester

2017-08

Type of Resource

text

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

Copyright and License Information

Copyright 2017 Zachery Matesich

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