Synthesis and conformational analysis of the plant hormone (auxin) related 2-(indol-3-yl)ethyl and 2-phenylethyl β-d-xylopyranosides and their 2,3,4-tri-O-acetyl derivatives

Abstract The synthesis, structure analysis by X-ray diffraction and NMR spectroscopy (including also 1 H 1 HNOE measurements), as well as molecular mechanics and dynamics of d -xylopyranose conjugates of 2-(indol-3-yl)ethanol (1) and 2-phenylethanol ( 2 ) are described. The per- O -acetylated derivatives of 2-(indol-3-yl)ethyl β- d -xylopyranoside (4β) and 2-phenylethyl β- d -xylopyranoside (7β) were prepared [along with corresponding α- d -isomers (4α and 7α) and 1,2- O -orthoacetates (5,8)] by Koenigs-Knorr condensation of the aglycone alcohols with 2,3,4- tri -O- acetyl -α- d - xylopyranosyl bromide. Glycoside 4β was deprotected to yield 2-(indol-3-yl) ethyl β- d -xylopyranoside (6). The crystal structures of 4β and 7β were determined. The crystals of both compounds are monoclinic, space group P 2 1 with a = 11.985(1), b = 7.317(1), c = 12.428(1) A . β = 93.2(1)°, Z = 2 (4β); a = 5.809(1), b = 19.833(1), c = 8.912(1) A , β = 106.0(1)°, Z = 2 (7β) . The β- d -xylopyranose rings are in the 4 C 1 chair conformation. The results of the theoretical conformational analysis are compared with the values obtained from the experimental measurements in solid state and solution.