Steric effects in the mass spectra of the stereoisomers of decalin-1,3-diol and of 1,3-dimethoxy-decalin

Abstract

The stereoisomers 1a–8a of decalin-1,3-diol have been synthesized by LAH-reduction of cis- and trans-decalin-1, 3-dione, respectively. With the exception of trans-decalin-1a,3e- and -1e,3a-diols, 7a and 8a, the stereoisomers have been isolated by column chromatography, and their configurations have been determined by 1H-NMR, IR and chemical methods. It is shown by the aid of deuterated derivatives, that the elimination of H 2O, MeOH and CH 2O from the molecular ions of the stereoisomeric diols and di-O-methyl ethers, respectively, occurs predominantly by stereospecific reactions, if the ground state conformation of the molecule corresponds to the geometry of the transition state of the elimination reaction. The steric control of the fragmentations is greatly reduced, if conformational changes of the molecular ions have to occur prior to fragmentation. No clear steric effects are observed, if none of the conformations of the intact molecular ions corresponds to the transition state. These steric effects can be used to identify the various stereoisomers of decalin-1,3-diol and 1,3-dimethoxy-decalin by mass spectrometry.