J Org Chem. 2021 Jan 1;86(1):980-994. doi: 10.1021/acs.joc.0c02480. Epub 2020 Dec 1.
We report here our results on the application of ynamides as substrates in the reactions with diorganyl dichalcogenides and iron(III) chloride to give selectively three different types of compounds: -α-chloro-β-(organoselenyl)enamides, 4-(organochalcogenyl)oxazolones, and vinyl tosylates. The results reveal that the selectivity in the formation of products was obtained by controlling the functional groups directly bonded to the nitrogen atom of the ynamides. Thus, α-chloro-β-(organoselenyl) enamide derivatives were exclusively obtained when the Ts- and Ms-ynamides were treated with a mixture of diorganyl diselenides (1.0 equiv) and FeCl (3.0 equiv) in dichloroethane (DCE, 3 mL), at room temperature. The 4-(organochalcogenyl)oxazolones were selectively obtained with ynamides having an ester group, directly bonded to the nitrogen atom, upon treatment with a solution of FeCl (1.5 equiv) and diorganyl dichalcogenides (1.0 equiv) in dichloromethane (3 mL) at room temperature. Finally, vinyl tosylates were obtained from ynamides having an ester group, directly bonded to the nitrogen atom, by reaction with -toluenesulfonic acid. We also studied the application of the prepared compounds as substrates for Suzuki and Sonogashira cross-coupling reactions.
我们在此报告了有关将酰亚胺作为底物与二芳基二硒化物和三氯化铁反应的结果，选择性地得到了三种不同类型的化合物：-α-氯-β-（芳基硒基）烯酰胺、4-（芳基杂化）噁唑酮和乙烯基对甲苯磺酸盐。结果表明，通过控制直接键合到酰亚胺氮原子上的官能团，可以获得产物形成的选择性。因此，当 Ts-和 Ms-酰亚胺与二芳基二硒化物（1.0 当量）和 FeCl（3.0 当量）的混合物在二氯乙烷（DCE，3 mL）中于室温下处理时，仅得到α-氯-β-（芳基硒基）烯酰胺衍生物。当具有直接键合到氮原子上的酯基的酰亚胺与三氯化铁（1.5 当量）和二芳基二硒化物（1.0 当量）在二氯甲烷（3 mL）中的溶液在室温下反应时，选择性地得到 4-（芳基杂化）噁唑酮。最后，通过酰亚胺与对甲苯磺酸的反应，得到了具有直接键合到氮原子上的酯基的乙烯基对甲苯磺酸盐。我们还研究了所制备的化合物作为 Suzuki 和 Sonogashira 交叉偶联反应底物的应用。
