Strong Axial Preference of 2-S Substituents in 3,4-Dihydro-2 H -1-Benzopyrans

The synthesis and crystal structure of a O,S,S-acetal derivative (1 R *,2 R *,2' S *)-1-(3,4-dihydro-2 H -1-benzopyran-2-ylthio)-2-phenyl-1-phenylthiopropan-2-ol 4 are reported. The 2-S-sidechain orientation in solution determined by OCHS signals in 1 H NMR spectra is mainly axial in all the 3,4-dihydro-2 H -1-benzopyran derivatives. Compound 4 crystallizes in the triclinic space group P 1 with an axial 2-S-sidechain and an intramolecular hydrogen bond between the OH and the ether oxygen with the O;;;O distance of 2.799(3) Å.