Formation of Five-Membered Carbocycles from d-Glucose: A Concise Synthesis of 4-Hydroxy-2-(hydroxymethyl)cyclopentenone

A concise synthesis of 4-hydroxy-2-(hydroxymethyl)cyclopentenone (1) has been accomplished from d-glucose by a three-step sequence that features a catalyst-free hydrothermal reaction of d-glucal, which is readily obtained from d-glucose. Optimization of the reaction conditions for synthesizing 1 was performed by changing the temperature and reaction time. The treatment of d-glucal under the optimal conditions, i.e., at 120 °C for 24 h, provided 1 in the highest isolated yield of 61%. 1 would become a versatile intermediate for the synthesis of various fine chemicals having a cyclopentenone structure from cellulosic biomass.