NKT cell-dependent glycolipid–peptide vaccines with potent anti-tumour activity† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03599b Click here for additional data file. Click here for additional data file.

General chemical synthesis methods. Anhydrous solvents were obtained commercially. Solvents required for oxime ligation coupling reactions were distilled from 2,4-dinitrophenylhydrazine immediately prior to use. Air-sensitive reactions were carried out under Ar. Thin layer chromatography (TLC) was performed on aluminium sheets coated with 60 F254 silica. Flash column chromatography was performed on Reveleris® silica cartridges (38.6 μm) or SiliCycle® silica gel (40 63 μm). NMR spectra were recorded on a Bruker 500 MHz spectrometer. 1H NMR spectra were referenced to tetramethylsilane at 0 ppm (internal standard) or to residual solvent peak (CHCl3 7.26 ppm, CHD2OD 3.31 ppm, CHD2(SO)CD3 2.50 ppm). 13C NMR spectra were referenced to tetramethylsilane at 0 ppm (internal standard) or to the deuterated solvent peak (CDCl3 77.0 ppm, CD3OD 49.0 ppm, (CD3)2SO 39.5 ppm). CDCl3-CD3OD solvent mixtures were always referenced to the methanol peak. High resolution electrospray ionization (ESI) mass spectra and HPLC-ESI-MSMS analyses were undertaken on a Waters Q-TOF PremierTM Tandem Mass spectrometer fitted with a Waters 2795 HPLC. Semipreparative HPLC and synthetic purity HPLC data were obtained on an Agilent 1100 system and peak identity was confirmed by LCMS on an Agilent 1260 HPLC with an Agilent 6130 single quadrupole mass spectroscopic detector using ESI. Each of these latter two systems was coupled to a Dionex Corona Ultra RS charged aerosol detector (CAD) as required. Fmoc-L-Leu-O-CH2-C6H4-OCH2-CH2-COOH linker was purchased from PolyPeptide Group (Strasbourg, France). Nα-9-Fluorenylmethoxycarbonyl (Fmoc) protected L-α-amino acids and 2-(6-chloro-1H-benzotriazole-1-yl)-1,1,3,3-tetramethylaminium hexafluorophosphate (HCTU) were purchased from GL Biochem (Shanghai, China). Dimethylformamide (DMF) and acetonitrile were purchased from Global Science (Auckland, NZ); 3,6dioxa-1,8-octanedithiol (DODT), triisopropylsilane (TIPS), diisopropylethylamine (DIPEA), and piperidine were purchased from Sigma Aldrich (St Louis, MO). Trifluoroacetic acid (TFA) was obtained from Oakwood Products, Inc (West Colombia, SC).