Conformation of 4-thio-L-lyxono-1,4-lactone in solution and in the crystalline state

Abstract

The conformation in 2H2O of 4-thio-L-lyxono-1,4-lactone (1) was studied by nuclear magnetic resonance spectroscopy, by means of homonuclear (J(1(H),1(H))) and heteronuclear (J(1(H),13(C))) coupling constants. The couplings were directly measured by a two-dimensional heteronucleus-coupled ω1 hetero-half-filtered proton-proton correlation (HETLOC) experiment, which does not require 13C isotopic enrichment. In solution, the thiolactone ring of 1 adopts preferentially the E3 conformation, and its hydroxymethyl group populates mainly the gt rotamer. The X-ray diffraction data of a single crystal of 1 indicates that also in the solid state the thiolactone ring adopts an E2 conformation, with a puckering somewhat larger than that observed for aldono-1,4-lactones and furanose rings. The molecules are linked by hydrogen bonds, which form chains. Particularly, O-5 is fully engaged as donor and acceptor in hydrogen bonding and the rotameric conformation of the hydroxymethyl group of 1 is fixed in