Copper‐Catalyzed Oxy‐Alkenylation of Homoallylic Alcohols to Generate Functional syn‐1,3‐Diol Derivatives

Abstract

A novel method for the synthesis of a wide range of functionalized 1,3‐diol derivatives is reported. Employing a copper‐catalyzed oxy‐alkenylation strategy, a range of readily available, substituted homoallylic alcohol derivatives and alkenyl(aryl) iodonium salts combine to form syn‐1,3‐carbonates in excellent yield and with high selectivity. Furthermore, the products formed are amenable to an iterative reaction sequence, thus affording highly complex polyketide‐like fragments.

Palladium-Catalyzed Stereoselective Cyclization of in Situ Formed Allenyl Hemiacetals: Synthesis of Rosuvastatin and Pitavastatin

“…Plenty of methods for the stereoselective synthesis of 1,3-diols have been developed: Allylation of β-hydroxyaldehydes, catalytic aldol reactions, stereoselective reduction, stereoselective hydrogenation, catalytic olefin carbonylation, biocatalytic methods, cyclization of homoallylic carbonates, Michael addition, tandem hemiacetal formation/Tsuji–Trost reation, catalytic oxy-alkenylation of homoallylic alcohols, or catalytic dehydrative allylation just to mention a few. We herein report a diastereoselective palladium-catalyzed intramolecular cyclization of in situ formed allenyl hemiacetals in order to access syn -configured methylene acetal protected 1,3-diols selectively.…”