A Convenient Approach to CF3-Containing N-Heterocycles Based on 2-Methoxy-2-methyl-5-(trifluoromethyl)furan-3(2H)-one

New synthetic routes to trifluoromethylated N‐heterocycles based on condensations of 2‐methoxy‐2‐methyl‐5‐(trifluoromethyl)furan‐3(2H)‐one with bifunctional N‐nucleophiles are described. For the first time, trifluoromethyl‐containing pyrazoles, pyrazolines and isoxazolines bearing hydrazone or oxime groups could be obtained by a one‐pot strategy based on reactions of 5‐(trifluoromethyl)furan‐3(2H)‐one with two equivalents of the corresponding hydrazines or hydroxylamine in the presence of an acid. The interaction of furan‐3(2H)‐one with ureas proceeded under mild conditions to furnish 1H‐furo[2,3‐d]imidazol‐2(3H)‐one derivatives in good yield. Further, a trifluoromethyl‐containing quinoxaline derivative was obtained by condensation of furan‐3(2H)‐one with ortho‐phenylenediamine. Reactions of the 2‐methoxy‐2‐methyl‐5‐(trifluoromethyl)furan‐3(2H)‐one with N‐binucleophiles are useful for the convenient preparation of trifluoromethyl‐containing pyrazoles, pyrazolines, quinoxalines, isoxazoles, 1H‐furo[2,3‐d]imidazol‐2(3H)‐ones.