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MAP-based multifunctional organocatalysts for asymmetric aza- and generic Morita–Baylis–Hillman reactions

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thesis
posted on 28.03.2022, 17:12 by Sviatoslav Sergeevich Eliseenko
MAP-based trifunctional organocatalysts, containing a phosphine Lewis base, amino Brønsted base, and phenol or N-tosyl Brønsted acid, have demonstrated highly proficient catalysis of asymmetric aza-MBH reactions with an acid additive. The phosphine nucleophile (Lewis base) initiates the aza-MBH reaction by addition to an activated alkene (e.g. MVK). The Brønsted base, activated by the acid additive, in conjunction with the Brønsted acid, promotes the subsequent aldol and proton-transfer elimination steps by H-bonding interactions to provide high rate and enantioselectivity. However, the reaction scope of this catalysis is limited to aza-MBH and not amenable to generic MBH reactions. In order to improve the proficiency and expand the substrate scope, new Brønsted acid motifs, such as substituted phenol, N-tosyl and pyrrole groups, were incorporated into the MAP-structure for testing in aza-MBH and generic MBH reactions. Change of Brønsted acidity in the phenol- and N-tosyl-containing catalysts did not improve on catalytic proficiency while pyrrole-containing catalysts provided the improvement in enantioselectivity in generic MBH reactions.

History

Table of Contents

1. Introduction -- 2. Experimental section -- 3. Results and discussion.

Notes

Empirical thesis. Bibliography: pages 52-55

Awarding Institution

Macquarie University

Degree Type

Thesis MRes

Degree

MRes, Macquarie University, Faculty of Science and Engineering, Department of Chemistry and Biomolecular Sciences

Department, Centre or School

Department of Chemistry and Biomolecular Sciences

Year of Award

2016

Principal Supervisor

Fei Liu

Rights

Copyright Sviatoslav Sergeevich Eliseenko 2016. Copyright disclaimer: http://mq.edu.au/library/copyright

Language

English

Extent

1 online resource (xvi, 55, SI i-xii pages) diagrams, tables

Former Identifiers

mq:55570 http://hdl.handle.net/1959.14/1150527