Bw. Gung et al., CONFORMATIONAL PREFERENCES OF C1-OXYGENATED ACYCLIC CHIRAL ALKENES - EVIDENCE FOR THE C-C ECLIPSED CONFORMER, Journal of organic chemistry, 58(12), 1993, pp. 3350-3354
Three forms of conformational minima were found for 3-buten-2-ol by ab
initio MO methods, including the conformers where the allyl methyl gr
oup eclipses the C=C bond. The computational results are corroborated
by a VT NMR study of a variety of Cl-oxygenated chiral alkenes. The ex
perimental study indicates that chiral allylic alcohols and ethers wit
h a formula of (E)-RCH=CHCH(OP)R' can have either two or three stable
rotamers depending on the size of the allylic substituent, R'. When R'
is a methyl group, the coupling constant, 3J(ab), is smaller than whe
n R' is a bulky group, indicating a three-rotamer equilibrium.