N-acetyl neuraminic acid is a derivative of neuraminic acid which is found at the terminal position of glycoconjugates at the exterior wall of the cell membranes. The biological functions of sialic acid containing glycoconjugates (sialosides) are were important, and therefore the chemical synthesis of these molecules has been a research goal in the field. The latter has seen a tremendous advancement towards synthetic methodologies for the synthesis of sialosides. However, due to a lack in the field of a comprehensive knowledge on the effect of O-protecting groups in sialylations, in the past years our research goal has been shifted into the systematic study of protecting/activating/stereodirecting groups at positions O-4, and O-7,8,and 9. Herein we report: a) the synthesis and testing of O-4 modified sialyl donors bearing several Silicon-based groups; b) the synthesis of O-4 Picoloylated sialyl donor by a regioselective acylation methodology; c) the testing of O-7 and O-9 Picoloylated sialyl donors. In addition, preliminary data on a collaborative study on sialylation reactions at room temperature is also described.