Pradeep Natarajan, Subhashini V. Subramaniam and Saravanan Peruncheralathan*,
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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.
期刊介绍:
The Journal of Organic Chemistry welcomes original contributions of fundamental research in all branches of the theory and practice of organic chemistry. In selecting manuscripts for publication, the editors place emphasis on the quality and novelty of the work, as well as the breadth of interest to the organic chemistry community.