Vinogradova Ekaterina V, Müller Peter, Buchwald Stephen L
Angew Chem Int Ed Engl. 2014 Mar 17;53(12):3125-8. doi: 10.1002/anie.201310897.
Hypervalent iodine λ3-benziodoxoles are common electrophilic transfer reagents known for their enhanced stability compared to their non-cyclic analogues. Herein we present data showing that chlorobenziodoxole reacts with two different thiolate nucleophiles (thiocyanate and trifluoromethylthiolate), resulting in the formation of stable thioperoxy complexes rather than the expected benziodoxole derivatives. We further report a revised structure for the earlier described electrophilic trifluoromethylthiolation reagent (1), which was previously believed to contain the benziodoxole framework. Our findings, which are based on a combination of analytical techniques, including the recently introduced crystalline sponge method for X-ray analysis, unambiguously demonstrate that 1 is a thioperoxy compound both in solution and the solid state.
高价碘λ3-苯并碘杂环戊二烯是常见的亲电转移试剂，与非环状类似物相比，其稳定性更高。在此，我们展示的数据表明，氯苯并碘杂环戊二烯与两种不同的硫醇盐亲核试剂（硫氰酸盐和三氟甲硫醇盐）反应，生成稳定的硫过氧配合物，而非预期的苯并碘杂环戊二烯衍生物。我们还报告了之前描述的亲电三氟甲硫基化试剂（1）的修正结构，该试剂此前被认为含有苯并碘杂环戊二烯骨架。我们基于多种分析技术的研究结果，包括最近引入的用于X射线分析的晶体海绵法，明确表明1在溶液和固态中均为硫过氧化合物。
