Facile Synthesis of Enantiopure Sugar Alcohols: Asymmetric Hydrogenation and Dynamic Kinetic Resolution Combined

Abstract An unprecedented Ir/f‐amphox‐catalyzed asymmetric hydrogenation of racemic 2,3‐ syn ‐dihydroxy‐1,4‐diones is presented involving dynamic kinetic resolution, which produces (1 R ,2 R ,3 R ,4 R )‐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 Fourier‐transform infrared spectroscopy and isolation of intermediates.