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Configurational effects in 17O NMR chemical shifts of hydroxyl-substituted, bicyclo [2.2.1]heptenes and -heptanes, their methylated derivatives and some related compounds

✍ Scribed by Erkki Kolehmainen; Katri Laihia


Publisher
John Wiley and Sons
Year
1993
Tongue
English
Weight
533 KB
Volume
31
Category
Article
ISSN
0749-1581

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✦ Synopsis


Abstract

Well resolved natural abundance ^17^O NMR spectra of 27 mono‐, di‐, tri‐ and tetrahydroxybicyclo[2.2.1]heptenes and ‐heptanes (norbornenes or norbornanes), their methylated derivatives and some related compounds were measured for 0.5 M or saturated solutions in acetonitrile at 65°C. In addition, the ^17^O NMR chemical shifts of 14 aliphatic and alicyclic alcohols were also determined for reference purposes. The ^17^O NMR chemical shifts of all compounds were assigned. Both methyl‐ and hydroxyl‐induced deshielding β‐effects were consistent with those reported in the literature. Similarly, observed shielding γ‐effects were in agreement with the earlier observations and characteristic especially for mutual γ‐gauche and ‐eclipsed orientations of substituents. In addition, clear shielding δ‐effects (up to 10 ppm) were observed in tri‐ or tetrahydroxynorbornanes. These δ‐effects can be related to the attractive van der Waals interactions observed earlier in ^13^C NMR chemical shifts.