State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.
Frontiers Science Center for New Organic Matter, Nankai University, Tianjin, 300192, China.
Nat Commun. 2022 Oct 28;13(1):6445. doi: 10.1038/s41467-022-34223-7.
Sulfur-heteroatom bonds such as S-S and S-N are found in a variety of natural products and often play important roles in biological processes. Despite their widespread applications, the synthesis of sulfenamides, which feature S-N bonds that may be cleaved under mild conditions, remains underdeveloped. Here, we report a method for synthesis of N-acyl sulfenamides via copper-catalyzed nitrene-mediated S-amidation reaction of thiols with dioxazolones. This method is efficient, convenient, and broadly applicable. Moreover, the resulting N-acetyl sulfenamides are highly effective S-sulfenylation reagents for the synthesis of unsymmetrical disulfides under mild conditions. The S-sulfenylation protocol enables facile access to sterically demanding disulfides that are difficult to synthesize by other means.
硫杂原子键，如 S-S 和 S-N，存在于各种天然产物中，并且在生物过程中经常发挥重要作用。尽管它们的应用广泛，但含 S-N 键的亚磺酰胺的合成仍不发达，该键在温和条件下可能会被切断。在这里，我们报告了一种通过铜催化氮宾介导的硫醇与二恶唑酮的 S-酰胺化反应合成 N-酰基亚磺酰胺的方法。该方法高效、方便且具有广泛的适用性。此外，得到的 N-乙酰亚磺酰胺是在温和条件下合成不对称二硫化物的高效 S-亚磺化试剂。该 S-亚磺化方案可以方便地获得空间位阻较大的二硫化物，这些二硫化物很难通过其他方法合成。
