Abstract
Reported herein is the first efficient strategy to synthesize a broad range of unsymmetrical N‐CF3 hydrazines, which served as platform to unlock numerous currently inaccessible derivatives, such as tri‐ and tetra‐substituted N‐CF3 hydrazines, hydrazones, sulfonyl hydrazines, and valuable N‐CF3 indoles. These compounds proved to be remarkably robust, being compatible with acids, bases, and a wide range of synthetic manipulations. The feasibility of RN(CF3)‐NH2 to function as a directing group in C−H functionalization is also showcased.
Highlights
Reported is the first efficient strategy to synthesize a broad range of unsymmetrical N-CF3 hydrazines, which served as platform to unlock numerous currently inaccessible derivatives, such as tri- and tetra-substituted NCF3 hydrazines, hydrazones, sulfonyl hydrazines, and valuable N-CF3 indoles
Our group previously developed a strategy to trifluoromethylate secondary amines,[14] we found that the application of the same protocol to N’-protected hydrazines was not a viable strategy to N-CF3 hydrazines, as the key thiocarbamoyl fluoride intermediate did not form
After examining various conditions, we uncovered that N-CF3 carbamoyl azide 2 forms the corresponding N-CF3 hydrazine 3 after heating at 100 8C for 3 days in aqueous THF[18] in 77 % yield
Summary
Reported is the first efficient strategy to synthesize a broad range of unsymmetrical N-CF3 hydrazines, which served as platform to unlock numerous currently inaccessible derivatives, such as tri- and tetra-substituted NCF3 hydrazines, hydrazones, sulfonyl hydrazines, and valuable N-CF3 indoles. To our delight, when we subsequently subjected sodium azide to 1 in THF for 16 hours at room temperature, we successfully formed the corresponding carbamoyl azide 2, which we isolated by filtration over celite in quantitative (98 %) yield (see Figure 2).
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