Synthesis and application of pinene-pyridine derivatives in asymmetric catalysis

Friscourt, Frederic (2008) Synthesis and application of pinene-pyridine derivatives in asymmetric catalysis. PhD thesis, University of Glasgow.

Abstract

The research described herein focuses on the synthesis of chiral pinene-pyridine derivatives, and their application in asymmetric catalysis. Both transition metal catalysed and organocatalytic transformations were investigated.

Chiral pyridine-phosphines based on α-pinene were synthesised and applied as efficient P,N-ligands for the enantioselective palladium(II)-catalysed Baeyer-Villiger oxidation of prochiral 3-substituted cyclobutanones to furnish chiral γ-butyrolactones in up to 81% ee. Complexes of these ligands with iridium can also promote asymmetric hydrogenation of olefins in up to 83% ee.

Novel N,N’-dioxides were synthesised from α-pinene and a range of 2-pyridine-acetophenones by employing Kröhnke annulation reaction as the key cyclisation step. Although poor enantioselectivity was achieved (up to 12% ee), high reactivity of the catalysts is, however, promising.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Asymmetric, catalysis, pinene, palladium, iridium, baeyer-villiger, hydrogenation, silicon, allylation
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Kocovsky, Prof. Pavel
• Date of Award: 2008
• Depositing User: Dr Frederic Friscourt
• Unique ID: glathesis:2008-532
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 02 Mar 2009
• Last Modified: 10 Dec 2012 13:19
• URI: https://theses.gla.ac.uk/id/eprint/532