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Permanent link (DOI): https://doi.org/10.7939/R3G956

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Developments and Mechanistic Investigations of Ester, Imide, and Ketone Hydrogenations Open Access

Descriptions

Other title
Subject/Keyword
imide
ketone
enantioselective
hydrogenation
ester
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Takebayashi, Satoshi
Supervisor and department
Bergens, Steven H. (Chemistry)
Examining committee member and department
Clive, Derrick L.J. (Chemistry)
Bergens, Steven H. (Chemistry)
Rivard, Eric (Chemistry)
Baker, R. Tom (Chemistry, University of Ottawa)
Cowie, Martin (Chemistry)
Semangia, Natalia (Chemical and Material Engineering)
Department
Department of Chemistry
Specialization

Date accepted
2012-05-31T10:10:19Z
Graduation date
2011-06
Degree
Doctor of Philosophy
Degree level
Doctoral
Abstract
The Noyori-type catalyst trans-[Ru((R)-BINAP)(H)2((R,R)-dpen)] (6) and its analogues are among the most active and enantioselective ketone hydrogenation systems reported to date. Its applications towards other types of carbonyl compounds are, however, understudied. This dissertation describes the first applications of this catalyst system towards hydrogenations of esters and imides under mild reaction conditions. Further, a detailed mechanistic study of this system is presented using ketones, esters, and imides as substrates. The dihydride 6 was highly active towards the hydrogenation of esters. Stoichiometric reactions between 6 and lactones proceeded at –80 °C to form the net hydride insertion products, Ru-hemiacetaloxides. The hemiacetaloxides were further hydrogenated at –40 °C under ~2 atm of H2 to form the corresponding Ru-alkoxides. Catalytic hydrogenations could be carried out, even at –20 °C under 4 atm of H2, however, these hydrogenations slowed over time due to deactivation of the catalyst by primary alcohol products. The first homogeneous monohydrogenation of imides was developed using 6 and related compounds as catalysts. Further, upon optimization of reaction conditions and imide structure, meso-cyclic imides were desymmetrized in high ee via the monohydrogenation to form kinetically unfavoured trans-hydroxy lactams with up to 5 stereogenic centres. Furthermore, the number of stereogenic centres was increased from 5 to 7 using N-acyliminium ion chemistry. A model for the origin of enantioselection was proposed using substrate-catalyst steric interactions. Low temperature NMR studies revealed that base catalyzes the rapid cis-trans isomerization to form the thermodynamically more stable trans-isomer. It was proposed that this rapid isomerization prevents racemization of a product. Transition states for the formation of Ru-alkoxides from addition between 6 and acetophenone were studied using an intramolecular trapping experiment. Addition between 6 and 4-hydroxymethylacetophenone at –80 °C exclusively formed the net hydride insertion product, Ru-secondary-alkoxide. Combined with controlled experiments, this result is strong evidence for the formation of a Ru–O interaction in the transition state, which supports concerted formation of the Ru-alkoxides from 6 and acetophenone.
Language
English
DOI
doi:10.7939/R3G956
Rights
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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