Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008 Supporting Information Conformationally armed glycosyl donors: Reactivity quantification, new donors and one pot reactions. Christian Marcus Pedersen, Lavinia G. Marinescu, and Mikael Bols 5 Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København Ø, Denmark. General Information: 13 C-, 1 H- and H,H-COSY NMR were recorded on a Varian Mercury 400 (400MHz) NMR Instruments. The spectra were referenced to solvent residues. ES-MS was recorded on a Micromass LC-TOF instrument and MALDI-TOF MS was recorded on a Bruker Deltronics mass 10 spectrometer using cinnamic acid (HCCA) based matrix. Optical rotations were measured on a PE-314 polarimeter at 20±1 °C. Chromatography was performed in Merck 60 silica. TLC was performed on Merck silica 60 E 254 coated glass plates and developed using Ce-mol (10 g Ce(IV)SO 4 and 15 g (NH 4 ) 2 MoO 4 in 1 L 10% H 2 SO 4 med ) or phosphomolybic acid (MoO 3 -H 3 PO 4 xH 2 O 5 % in EtOH) and subsequent heating. 15 Figure S1. Glycosylation reactivities of different types of donors. 20 Determining the relative rate of glycosylation: Each reaction was performed on 6 samples of 2 mL; each sample contained a solution of the appropriate donor in dichloromethane (different 0 0.002 0.004 0.006 0.008 0.01 0.012 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 concentration [mM] substrate rate [mM/s] O SPh OTBS TBSO OTBS O OBn BnO BnO OBn SPh O OAc AcO AcO OAc SPh