β‑Selective\n2‑Deoxy- and 2,6-Dideoxyglucosylations\nCatalyzed by Bis-Thioureas

We\npresent methods for β-selective 2-deoxy- and 2,6-dideoxyglucosylations\nof natural products, carbohydrates, and amino acids using bis-thiourea\nhydrogen-bond-donor catalysts. Disarming ester protecting groups were\nnecessary to counter the high reactivity of 2-deoxyglycosyl electrophiles\ntoward non-stereospecific S<sub>N</sub>1 pathways. Alcohol and phenol\nnucleophiles with both base- and acid-sensitive functionalities were\ncompatible with the catalytic protocol, enabling access to a wide\narray of 2-deoxy-β-<i>O</i>-glucosides.