Our group previously developed stereospecific β-glycosylations with glycosyl phosphates promoted by bis-thiourea hydrogen-bond-donor (HBD) catalysts. Extensive experimental and computational evidence has been advanced consistent with a mechanism of substitution involving dual activation of both the electrophile and nucleophile via general acid/base interactions (Figure ). Precise geometrical preorganization and matching of the hydrogenbond-donating and -accepting domains of the catalysts were critical for achieving high levels of stereospecificity. Here, we report the successful extension of this dual activation strategy to β-selective 2-deoxy-and 2,6-dideoxyglucosylations of amino acids, carbohydrates, natural products, and pharmaceuticals. The approach relies on precise tuning of the bis-thiourea catalysts together with utilization of precisely tuned phosphate leaving groups and disarming protecting groups to attenuate the inherent reactivity of the deoxy-and dideoxy-glucosyl electrophiles.