Nucleophilic addition of thiols to N , N -bis(oxy)enamines (nitrosoalkene acetals) produce valuable α-thiooximes in a highly efficient manner. The reaction was found to be solvent-dependent, likely because of distinct mechanisms operating in nonpolar and basic solvents (involving either Bronsted acid or Lewis base catalysis). By performing a series of competition experiments, the relative reactivity of S-, N-, and O-nucleophiles in reaction with N , N -bis(oxy)enamines was determined for the first time. Interestingly, the relative nucleophilicity was found to be highly dependent on the solvent, which allows regioselective control of these reactions by using an appropriate medium.

中文翻译：

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通过将硫醇加成到 N,N-双(氧基)-烯胺中来合成 α-硫肟：S-、N-和 O-亲核试剂与亚硝基烯烃物质的迈克尔反应的比较研究

硫醇与 N，N-双（氧）烯胺（亚硝基烯烃缩醛）的亲核加成以高效的方式产生有价值的 α-硫肟。发现该反应依赖于溶剂，可能是因为在非极性和碱性溶剂（涉及布朗斯台德酸或路易斯碱催化）中运行的不同机制。通过进行一系列竞争实验，首次测定了 S-、N-和 O-亲核试剂与 N、N-双（氧）烯胺反应的相对反应性。有趣的是，发现相对亲核性高度依赖于溶剂，这允许通过使用适当的介质对这些反应进行区域选择性控制。