Angewandte Chemie, Accepted Article.
Presented herein is an unprecedented Ir/f‐amphox‐catalyzed asymmetric hydrogenation of racemic 2,3‐syn‐dihydroxy‐1,4‐diones via dynamic kinetic resolution to produce (1R,2R,3R,4R)‐tetraols. This protocol constitutes an efficient and straightforward approach to accessing sugar alcohols bearing four contiguous stereocenters. The strategy exhibits various advantages over existing methods, including excellent yields (up to 98%), exceptional stereoselectivities (up to 99:1 dr, 99.9% ee), operational simplicity and substrate generality. Moreover, the nature of the reaction was revealed as a stepwise transformation by in situ FTIR spectroscopy and isolation of intermediates.