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When unsubstituted thiophenol was used instead ofp\u2010nitrothiophenol as a component of the disulfide substrate the thioglycoside was obtained in low yield and a large amount of the anomeric thiol was formed (see theSupporting Information)."},{"key":"e_1_2_2_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja072969u"},{"key":"e_1_2_2_34_2","unstructured":"Cysteine epimerization as opposed to carbohydrate anomerization was established through the complete assignment of the NMR spectrum including the critical observation of two distinct signals for 1\u2010H\u03b2."},{"key":"e_1_2_2_35_2","unstructured":"Similar yields were observed with hexaethylphosphorus triamide; however the purification of the product was more cumbersome than when HMPT was used."},{"key":"e_1_2_2_36_2","unstructured":"Crossover experiments on differentially protected glycosyl cysteine derivatives under the optimized reaction conditions revealed that glycosyl exchange takes place and thus lent support for a dehydroalanine intermediate.1H\u2005NMR spectroscopic analysis allowed the direct observation of dehydroalanine formation and consumption (see theSupporting Informationfor details). The low diastereoselectivity in the subsequent conjugate addition is consistent with that previously reported in reference\u2005[10]."},{"key":"e_1_2_2_37_2","unstructured":"Other \u03b1\u2005centers in the peptide did not undergo epimerization which suggests that the observed epimerization at the \u03b1\u2005center of cysteine derives largely if not exclusively from dehydroalanine formation and not from deprotonation by HMPT."},{"key":"e_1_2_2_38_2","unstructured":"The diastereoselectivity of the reaction in Figure\u20051 will depend on the stereochemical environment of C156. 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