Bisset, Alexander A. (2013) Studies on asymmetric approaches to (-)-cytisine and related molecules. PhD thesis, University of Warwick.

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Abstract

In this project, the asymmetric pressure and transfer hydrogenation of a number of
substrates was carried out in attempt to asymmetrically form 5-substituted 6-
membered saturated heterocycles, directly applicable to the asymmetric synthesis of
(-)-cytisine and other related compounds. The hydrogenation of N-acylaminoacrylate-
like enamide 1 was successful, resulting in the formation of 5-
substituted glutarimide 218 in up to 94 % ee. Unfortunately, subsequent reduction
resulted in epimerisation and loss of ee, preventing an asymmetric synthesis of (-)-
cytisine precursor 5. The asymmetric reduction of pyridones 2 and 3 (featuring
proximal coordinating groups) did not proceed with any enantioselectivity; however,
the racemic reduction products were successfully utilised in novel syntheses of
cytisine precursor 5 and bispiperidine 6 respectively. The ATH of pyridyl methyl
ketone 4 with (R,R)-RutethTsDPEN, (R,R)-248 resulted in the formation of pyridyl
alcohol 303 in 78-83 % ee. This compound was converted to diastereomers (D1)-7a
and (D2)-7b which are derivates of a cytisine precursor and other therapeutic targets.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Asymmetric synthesis, Cytisine, Hydrogenation
Official Date:	February 2013
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Wills, Martin
Sponsors:	AstraZeneca (Firm)
Extent:	288 leaves : illustrations.
Language:	eng

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