Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans

Greaney, Liam

Restricted to everyone for five years. Restriction lift date: 2021-10-13T11:14:36Z

Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans

dc.check.date	2021-10-13T11:14:36Z
dc.check.embargoformat	Both hard copy thesis and e-thesis	en
dc.check.entireThesis	Entire Thesis Restricted
dc.check.info	Restricted to everyone for five years	en
dc.check.opt-out	No	en
dc.check.reason	This thesis is due for publication or the author is actively seeking to publish this material	en
dc.contributor.advisor	Maguire, Anita R.	en
dc.contributor.advisor	Mccarthy, Daniel G.	en
dc.contributor.author	Greaney, Liam
dc.contributor.funder	Cork County Council	en
dc.date.accessioned	2016-10-14T11:14:36Z
dc.date.issued	2015
dc.date.submitted	2015
dc.description.abstract	The research described in this thesis is concerned with the synthesis and stereoselective transformations of 4,5-dihydro-3(2H)-furanones and their 3-hydroxy derivatives. In Chapter 1, a review of synthetic routes to 3-hydroxytetrahydrofurans is presented. This incorporates the wide range of applications for these types of compounds. Preparative routes to and stereoselective transformations of the furanones investigated in this study are discussed in Chapter 2. The bulk of the work centers on stereoselective carbonyl group reductions to generate the 3-hydroxytetrahydrofuran derivatives in racemic form followed by kinetic resolution via lipase mediated esterification, resulting in enantioenriched 3-acetoxy and 3-hydroxytetrahydrofuran derivatives. In many cases, these processes proceed in a highly enantioselective manner. The influence of the lipase species and concentration of enzyme employed on the yield and stereochemical outcome of the reactions is examined in detail. Access to the complementary series of furanone and hydroxytetrahydrofuran derivatives by oxidation or reduction of the enantioenriched compounds was achieved through conventional synthetic methods. Chapter 2 also contains details of a novel synthetic route to a range of 2,3,5-trisubstituted furans from α-hydroxyenones and 4,5-dihydro-3(2H)-furanones. The mechanistic rationale for these transformations and the migratory aptitude of alkyl groups towards the formation of these furans is discussed in detail. Finally, Chapter 2 outlines the synthesis of a series of diarylcyclopentenones that were synthesised as part of our investigations. Chapter 3 contains a description of the synthetic procedures and biotransformations carried out together with key analytical and spectroscopic properties of the compounds studied and where appropriate, their analysis using chiral HPLC analysis.	en
dc.description.status	Not peer reviewed	en
dc.description.version	Accepted Version
dc.format.mimetype	application/pdf	en
dc.identifier.citation	Greaney, L. 2015. Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans. PhD Thesis, University College Cork.	en
dc.identifier.endpage	261	en
dc.identifier.uri	https://hdl.handle.net/10468/3182
dc.language.iso	en	en
dc.publisher	University College Cork	en
dc.rights	© 2015, Liam Greaney.	en
dc.rights.uri	http://creativecommons.org/licenses/by-nc-nd/3.0/	en
dc.subject	3-Hydroxytetrahydrofurans	en
dc.subject	Chemoenzymatic synthesis	en
dc.thesis.opt-out	false
dc.title	Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans	en
dc.type	Doctoral thesis	en
dc.type.qualificationlevel	Doctoral	en
dc.type.qualificationname	PhD (Science)	en
ucc.workflow.supervisor	a.maguire@ucc.ie