Synthesis and application of pinene-pyridine derivatives in asymmetric catalysis.
PhD thesis, University of Glasgow.
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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.
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