Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 Glycoligands and Co(II) glycocomplexes. Investigation of the variation of the sugar-scaffold on the structure and chirality measured by circular dichroism. Federico Cisnetti, Régis Guillot, Michel Desmadril, Giorgio Pelosi, Clotilde Policar 1. Synthesis and characterizations. NMR analysis were performed on a Bruker AV360 spectrometer, IR spectra were recorded on a Bruker IFS66, ES-MS were recorded on a Finnigan Mat 95S in a BE configuration at low resolution. Microanalysis have been recorded at the CNRS-Gif sur Yvette (CHNO) and CNRS-Vernaison (CoClP). 1,2-O-isopropylidene-α-D-glucofuranose (resp. 1,2-O-isopropylidene-α-L-glucofuranose) was obtained by selective hydrolysis of 1,2,5,6-di-O-isopropylidene-α-D-glucofuranose (resp. 1,2,5,6-di-O-isopropylidene-α-L-glucofuranose). 1 Methyl α-D-lyxofuranoside was obtained in one step from D-lyxose using Van Boom et al. protocol. 2 Reagents and solvents were purchased from Acros and used without further purfication. General picolylation protocol (adapted from Szeja et al. benzylation protocol 3 ) The quantities are given typically in the case of 2.5 mmol of the triol derivative. The triol derivative (2.5 mmol) was dissolved in DMSO (1 mL). 2-picolyl chloride hydrochloride (9 mmol, 3.6 eq.) was suspended in toluene (5 mL). Neutralisation and concomitant extraction in the toluene phase of the picolyl chloride was performed by pouring sat. Na 2 CO 3 on this suspension until gaseous evolution ceased. The aqueous phase was decanted and the organic phase was added to the triol solution. 0.1 eq. (0.25 mmol) of (NBu 4 ) + (HSO 3 ) – , 0.1 mL of t- amyl alcohol and 2.5 g of a 4:1 ground mixture of K 2 CO 3 and NaOH were added to the reaction mixture which was vigourously stirred overnight after which TLC analysis (AcOEt / MeOH 9:1) showed in all cases the complete disappearance of the starting triol compound. The products were recovered by extraction (dichloromethane/water) followed by solvent evaporation and column chromatography (elution gradient: AcOEt to AcOEt / MeOH 9:1). 1,2-O-isopropylidene-3,5,6-tri-O-(2-picolyl)-α-D-glucofuranose L3 and 1,2-O- isopropylidene-3,5,6-tri-O-(2-picolyl)-α-L-glucofuranose L3’ 1.085 g, yield: 87% as an hygroscopic oil for L3, 200 mg, 60% as an hygroscopic oil for L3’ 1 H-NMR : δ (ppm) = 8.5 (m, 3H, H 2py s) , 7.6 (m, 3H, H 4py s), {7.50 (d, J=7.8 Hz, 1H), 7.43 (d J=7.8Hz, 1H), 7.36 (d, J = 7.8 Hz, 1H)} (H 5py ), 7,1 (m, 3H, H 3py s), 5.93 (d, J= 3.8 Hz, H 1 ), {4.99 (d, J=13.2 Hz, 1H, 4.8-4.6, m, 6H} (H 2 , CH 2pic s), 4.42 (dd, J 1 =9.3 Hz, J 2 =3.1 Hz, 1H, H 4 ), 4.23 (d, J=3.1, 1H, H 3 ), 4.18 (ddd J 1 =9.3 Hz, J 2 =5.6 Hz ,J 3 =1.9 Hz, H 5 ), {4.05 (dd J 1 =10.7 Hz, J 2 =1.9 Hz,1H), 3.83 (dd, J 1 =10.7 Hz, J 2 =5.6 Hz)} (H 6a and H 6b ) 13 C-NMR : δ (ppm) = {158.8, 158.7, 157.5} (C 2py s) , {149.0, 148.9, 148.8} (C 6py s), {136.7, 136.6, 136.5} (C 4py s), {122.5, 121.1(2C), 124.4, 121.2(2Cs)} (C 5py s, C 3py s), 111.8 (C quat.ip ), 105.2 (C 1 ), {82.2, 81.6, 78.8, 76.6} (CH 2pic s, C 6 ), {74.3.2, 73.6, 72.7, 71.6} (C 2 , C 3 , C 4 , C 5 ), {26.8, 26.3} (Me ip s) ES – MS : 494.2 (M+H) + , 35%, 516.2 (M+Na) + , 100% microanalysis (C 27 H 31 N 3 O 6 .0.5H 2 O calc/found) C (64.53/64.08), H (6.42/6.35), N (8.36/8.31), O (20.69/19.85) Methyl 2,3,5-tri-O-(2-picolyl)-α-D-lyxofuranoside L4 885 mg ; yield : 81% as a white polycrystalline solid.