Absolute configuration assignment of norcamphor-derived furyl hydroperoxide using density functional theory calculations of optical rotation and vibrational circular dichroism.

Density functional theory (DFT) calculations of sodium d line specific rotation and of vibrational circular dichroism (VCD) have been used to assign the absolute configuration of a recently prepared (1S,4R)-norcamphor-derived furyl hydroperoxide, (+)-3, introduced as a stereoselective oxidant. Both approaches give the same absolute configuration to the newly generated stereogenic carbon at position 2, i.e., (1S,2S,4R)-(+)-3, thus providing a confident assignment in a case made difficult by the large conformational flexibility and the small difference between the computed optical rotations of the two possible diastereoisomers. Although the computed IR absorption spectra of (1S,2S,4R)-3 and (1S,2R,4R)-3 are practically indistinguishable, a number of significant differences in the VCD spectra of these two nonmirror-image isomers can be observed, which allows the structural identification of the synthesized compound. This is clearly shown here for the first time.