P. Brun, J. Casanova, M. Raju
Jul 1, 1987
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Influential Citations
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Journal
Magnetic Resonance in Chemistry
Abstract
The complete analysis of the 13C NMR spectra of 30 cedrane derivatives with various functionalities on the 2, 6, 6, 8‐tetramethyltricyclo[5.3.11,701,5]undecane skeleton is reported. The assignment of the signals to the appropriate carbons has been made using the various functionalities on the molecular framework and the chemical shift theory (α, β, γ effects). When necessary, off‐resonance decoupling, INEPT and DEPT experiments have been used, as well as specific deuterium labelling. The last ambiguities were resolved with the aid of lanthanide shift reagents and SFORD experiments. The assignments for the reference compounds neoisocedranol oxide, cedrol and cedrene were made using the carbon‐carbon connectivity 2D INADEQUATE pulse sequence. The examination of cedrane derivatives functionalized on C‐9 (carbonyl, hydroxyl, acetate) and C‐8 (methyl, axial or equatorial) showed that the 13C chemical shifts of C‐5, ‐6, ‐11 and ‐13 are sensitive probes for the conformation of the six‐membered ring (ring C), which is essentially a flattened chair, and for the stereochemistry of the C‐8 and C‐9 substituents. Comparison with 2‐methylbicyclo[3.2.1]octan‐3‐ones shows that the Anti Reflex effect is operative in cedrane derivatives.