We herein report enantio- and diastereoselective fluorination of naphthoresorcinol and resorcinol derivatives for the first time using a dicarboxylate phase-transfer catalyst. Stereoselective oxidative transformation of resorcinol derivatives is considered to be difficult because of their high reactivity, multiple reaction sites, and multiple hydrogen bond interactions due to the presence of the two hydroxy groups. Even though resorcinol and its oxidized frameworks are widely found in bioactive natural compounds, dearomative asymmetric fluorination of resorcinol derivatives remains unexplored. We found that our chiral dicarboxylate phase-transfer catalyst could serve as an effective catalyst for the purpose. Interestingly, naphthoresorcinols and resorcinols were converted to difluorination products preferentially rather than monofluorinated products. It is noteworthy that asymmetric desymmetrization of symmetrically substituted resorcinols occurred with up to 95% ee and the reaction was tolerant of various functional groups.

我们在此首次报道了使用二羧酸相转移催化剂对萘基间苯二酚和间苯二酚衍生物进行对映选择性和非对映选择性氟化。间苯二酚衍生物的立体选择性氧化转化被认为是困难的，因为它们具有高反应性、多个反应位点以及由于两个羟基的存在而导致的多个氢键相互作用。尽管间苯二酚及其氧化骨架广泛存在于生物活性天然化合物中，但间苯二酚衍生物的脱芳基不对称氟化仍未得到探索。我们发现我们的手性二羧酸相转移催化剂可以作为一种有效的催化剂。有趣的是，萘并间苯二酚和间苯二酚优先转化为二氟化产物而不是单氟化产物。值得注意的是，对称取代的间苯二酚发生不对称去对称化，ee 高达 95%，并且反应对各种官能团具有耐受性。