Enantioselective Organocatalytic Desymmetric Acylation as an Access to Orthogonally Protected myo-Inositols.

Chiral cyclitols represent an important class of naturally occurring compounds. In particular, myo-inositol and its derivatives are essential for phosphorus storage and cell-signaling pathways in living organisms. Not surprisingly, these compounds constitute an emerging class of molecules with significant potential in both medicinal and synthetic chemistry. However, efficient catalytic methodologies for accessing chiral myo-inositol derivatives remain scarce. Herein, we report a metal-free, organocatalytic protocol for the desymmetric acylation of a readily available meso-myo-inositol diol. The reaction proceeds with high enantioselectivity, moderate to high yields, and broad tolerance to various functional groups. The developed methodology enables the efficient synthesis of chiral myo-inositol derivatives. Furthermore, its scalability and subsequent transformations into orthogonally protected building blocks for synthesizing myo-inositol phosphates underscore the practical utility of this approach.