Breaking the Symmetry of a Compound by Isotopic Substitution: Synthesis and Stereochemical Assignment of Monodeuterated -Perhydroazulene.

We report the synthesis and absolute configuration of monodeuterated -perhydroazulene (-), which is a rare example of an isotopically chiral hydrocarbon whose synthesis and stereochemical analysis are known to be particularly difficult. The synthesis features nickel-boride-catalyzed deuteration that allowed formation of the diastereomerically pure -fused bicyclic system in -. The vibrational circular dichroism results are in excellent agreement with the computed spectrum at ωB97XD/aug-cc-pVTZ, allowing unambiguous assignment of the absolute configuration of -.