Improved Chemistry of myo‐Inositol: a New Synthetic Strategy to Protected 1‐Keto‐ and 1,2‐Keto‐derivatives

Abstract

A refresh and improvement of the well‐known myo‐inositol chemistry is reported here, setting up a new synthetic protocol to obtain orthogonally protected compounds, with a special focus on the preparation of 2‐O‐alkylated compounds. A gram scale synthesis of the 2‐allyl compound was performed and optimized in terms of yield. This intermediate is the precursor of chiro‐1‐inosose, for which synthetic procedures are lacking. Taking advantage of the easily handled allyl group, we were able to transform this keto compound into both the 1,2‐diketone and 3‐deoxy‐1,2‐diketone, intermediates of biological transformations used in several patented applications. Finally, to access poly‐hydroxylated‐(aminomethyl)cyclohexane compounds, the reaction of the keto compound with cyanide was optimized, affording cyanohydrins obtained as single stereoisomer, the precursor of the above compound.