The origin of the high α (1, 2-cis)-stereoselectivity in the reaction of galactosyl and galactosaminyl donors with a di-tert-butylsilylene (DTBS) group with several nucleophiles has been elucidated by means of experimental and computational approaches. DTBS overcomes any other cyclic protecting groups examined to date and the β (1, 2-trans)- directing effect due to the neighboring participation by CO groups at C2. Requirements for ...