A new class of bifunctional linchpins bearing electrophilic sites beta or gamma to a silyl group have been designed, synthesized, and demonstrated to be competent in tricomponent unions exploiting Type II Anion Relay Chemistry (ARC). High diastereoselectivities were observed when a phenyl moiety (R(2)) served as an anion-stabilizing group (ASG) adjacent to a methyl susbtituent (R(1)), while diastereomeric mixtures were obtained when a phenylthiol moiety served as the ASG, irrespective of alpha-substitution.