Organocatalytic Dearomatization of 5-Aminopyrazoles: Synthesis of 4-Hydroxypyrazolines.

Dearomatization is a fundamental chemical reaction that affords complex three-dimensional heterocyclic frameworks. We disclose the first organocatalytic dearomatization of 5-aminopyrazoles, which yields a range of structurally diversified C4-hydroxylated pyrazolines with yields of ≤95% in <1.5 h at room temperature. This catalytic process is achieved using in situ -generated hypervalent iodine. The method also yields a spirolactone via an intramolecular dearomatization process. Furthermore, we demonstrate that substrate-directed reduction of the resulting iminopyrazoline leads to 4,5-difunctionalized pyrazoline as a single diastereomer. Mechanistic studies suggest that the reaction proceeds through a dearomatized cationic intermediate.