  To all appearances, electron impact mass spectrometer (EI-MS) is considered a
"chirally blind" instrument. Yet, numerous non-identical R (right) and S (left)
configurations of prochiral alcohols' mass spectra alcohols have appeared in
the literature with almost no justification. Such observations are often
attributed to impurities, experimental circumstances, inaccurate measurements,
etc. In an experimental attempt to explain this phenomenon, here we have
avoided the above mentioned pitfalls by conducting control experiments using
different pure enantiomers under the same circumstances. Hence, we report the
mass spectra of R- and S-enantiomers of 2-octanol (1R, 1S) and 1-octyn-3-ol
(2R, 2S) collected by running 20 independent experiments for each R- and
S-enantiomer. Statistical analyses confirmed that the peak intensities were
significant to an acceptable level of confidence. The 1R and 1S enantiomers
were separated reasonably in the PC space, implying that the chirally blind
EI-MS is able to discriminate between R and S prochiral alcohols.
Theoretically, self-complexation through H-bonding for S (or R) appears to give
a new chiral center at the H-bonded oxygen atom, producing a new dimeric pair
of diastereomers SRS and SSS (or RRR and RSR) before ionization, and SRS.+ and
SSS.+ (or RRR.+ and RSR.+) after ionization. The results of our calculations
have explicitly shown that these hydrogen bonds formed. Interestingly, the
latter four ionized diastereomers appear with different structural and
thermodynamic parameters at the M06-2X/6-311++g (d,p) level of theory.
