*3.1. General Procedures*

1H-, 13C-NMR, <sup>1</sup>Н, <sup>1</sup>Н-COSY, HSQC, HMBC, NOESY (Nuclear Overhauser Effect Spectroscopy), and TOCSY spectra (in CD3OD or CDCl3) were recorded on Bruker Avance III HD 500 and Bruker Avance III 700 spectrometers (Bruker BioSpin, Bremen, Germany) at 125 MHz (13C), 500 (1H), and 700 ( 1H) MHz. Chemical shifts (ppm) were internally referenced to the corresponding residual solvent signals δ<sup>H</sup> 3.306/ δ<sup>C</sup> 49.6 for CD3OD. For the spectra of compounds in CDCl3, TMS was used as an internal standard. ESI mass spectra were recorded on a Q-TOF 6510 mass spectrometer (Agilent Technologies, Santa Clara, CA, USA). GC-MS analyses were carried out on a Hewlett Packard HP6890 GC System (Hewlett-Packard Company, Palo Alto, CA, USA) with an HP-5MS (J&W Scientific, Folsom, CA, USA) capillary column (30.0 m × 0.25 mm), helium as the carrier gas, and 70 eV ionizing potential. GC analyses were done on an Agilent 6850 Series GC System chromatograph (Agilent Technologies, Santa Clara, CA, USA) equipped with an HP-1 (Agilent technology, Santa Clara, CA, USA) capillary column (30 m × 0.32 mm), the carrier gas was helium (flow rate 1.7 mL/min), and the detector temperature was 300 ◦C (or 280 ◦C for per-acetylated (2*R*)-oct-2-yl glucosides). The GC-MS analyses of FA esters and per-acetylated sphingoid bases were done using the injector temperature of 270 ◦C and the temperature program 100 ◦C (1 min)–10 ◦C/min–280 ◦C (30 min). The GC analyses of per-acetylated (2*R*)-oct-2-yl derivatives of D-Glc and L-Glc were carried out using the injector temperature of 150 ◦C and the temperature program 100 ◦C (0.5 min)–5 ◦C/min–250 ◦C (10 min). Optical rotation was measured on a Perkin–Elmer polarimeter, model 343 (Perkin-Elmer

GmbH, Überlingen, Germany). Column chromatography was performed using silica gel (50/100 μm, Sorbpolimer, Krasnodar, Russia). RP-HPLC separations were performed using a Du Pont Series 8800 Instrument (DuPont, Wilmington, DE, USA) with an RIDK-102 refractometer (Laboratorni pristroje, Praha, Czechoslovakia). Two columns (Agilent Technologies, Santa Clara, CA, USA), Agilent ZORBAX Eclipse XDB-C8 (4 × 150 mm), and Agilent ZORBAX SB-C18 (4.6 × 250 mm), were used for the HPLC.
