Synthesis and application of pinene-pyridine derivatives in asymmetric catalysis

QD Chemistry

Friscourt, Frederic ; Kocovsky, Pavel

University:University of Glasgow

Department:School of Chemistry

关键词: Asymmetric, catalysis, pinene, palladium, iridium, baeyer-villiger, hydrogenation, silicon, allylation;   

Others  :  http://theses.gla.ac.uk/532/1/2008friscourt1phd.pdf

来源: University of Glasgow

【 摘 要 】

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.