Use of a Lanthanide Shift Reagent for Simplified NMR Analysis of Borneol—Isoborneol Mixtures. Apparent Catalysis of OH Proton Exchange by LSR

The use of ¹H NMR at low field (60 MHz spectrometer frequency) for direct analysis of mixtures of borneol, 1, and isoborneol, 2, is considerably simplified by addition of the lanthanide shift reagent (LSR), tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium(III), 3. The effect of added 3 is twofold. Firstly, the analytical marker signals of the methine proton CHOH in 1 and 2, which are partly overlapped at 60 MHz in CDCl₃ (28°), are separated and rendered baseline-resolved due to preferential LSR binding to the less hindered endo OH of 1. Secondly, the absorption signals of the CHOH methines actually sharpen in the presence of 3, and display clearly defined multiplet structure, attributed to full exchange decoupling of the vicinal OH as a result of enhanced OH exchange rates when LSR is present.