Intrigued by these results, our focus shifted to the synthesis of polyfluorinated alkyl ethers. Initially, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), as the alcohol partner, yielded the desired product in only 37% yield under standard conditions. To enhance the yield, we made slight modifications: replacing the base with K 2 CO 3 and using 390 nm Kessil lamps (please see Table , supporting information). This adjustment led to the synthesis of polyfluorinated alkyl ethers in excellent yield (90%). Using these optimized conditions, we explored a broad range of polyfluorinated alcohols. The etherification between N-tosylhydrazones (1b) and primary polyfluorinated alcohols, such as 2,2,2-trifluoroethanol, pentafluoro-1-propanol, and 2,3,4,5,6-pentafluorobenzyl alcohol, demonstrated moderate to excellent reactivities (66d-73d). Furthermore, the secondary polyfluorinated alcohols, such as 1-phenyltrifluoroethanol, were compatible to produce the desired ether (74d). Inspired by this compatibility, various tertiary polyfluorinated alcohols, including 2-trifluoromethyl-2-propanol, hexafluoro-2methylisopropanol, and 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, were investigated and suitable for coupling in our system (75d-77d). Trichloroethanol, a polyhalogenated alcohol, underwent the smooth etherification to produce the corresponding ether (78d). In this context, the excess amounts of certain alcohols were required for the reaction (70d-72d), which was supposed that the decreased nucleophilicity caused by the increased number of fluorine atoms made the construction of the corresponding ethers more challenging. We further explored the scope of N-tosylhydrazones to assess the generality of this strategy and investigated the tolerance of N-tosylhydrazones to various electron-withdrawing or electrondonating groups (79d-88d). The mono-and multi-substituted N-tosylhydrazones derived from acetophenones yielded the desired polyfluorinated ethers in moderate to excellent yields. The Ntosylhydrazones containing naphthalenes or phenanthrenes with different substituents also provided the desired products (89d-91d). Furthermore, the N-tosylhydrazones with varying alkyl chain lengths exhibited moderate to good reactivities (92d-94d, 53-75%). The N-tosylhydrazones derived from diverse cyclic ketones, including 1-tetralone and 1-indanone, provided their corresponding ethers in excellent yields (95d, 96d). In addition, the N-tosylhydrazones derived from benzophenone and benzaldehyde demonstrated the good reactivities (97d, 98d). Notably, reducing the quantity of HFIP to 3.5 equivalents when using benzophenone-derived N-tosylhydrazone suggested that the aryl-aryl diazo intermediates were susceptible to O-H insertions. Furthermore, the system tolerated N-tosylhydrazones substituted