Synthesis ( IF 2.2 ) Pub Date : 2017-09-12 , DOI: 10.1055/s-0036-1590904 Xiaochun Yu , Shun Wang , Weijie Ding , Juan Hu , Huile Jin
Abstract
A general method for the synthesis of α,β-unsaturated esters, ketones, and nitriles is successfully achieved by a one-pot copper-catalyzed oxidation with O2 in air as oxidant. The solvent mixture of acetonitrile and formamide (1:1) is optimized to ensure the oxidation of alcohols, deprotonation of phosphonium salt, and Wittig reaction occur efficiently in one pot. A broad range of substrates has been explored for this process, including three electron-withdrawing group (CO2Et, COPh, CN) functionalized phosphonium salts. They reacted not only with benzylic and heteroaromatic alcohols, but also with aliphatic alcohols, forming the corresponding α,β-unsaturated esters, ketones, and nitriles in moderate to excellent yields.
A general method for the synthesis of α,β-unsaturated esters, ketones, and nitriles is successfully achieved by a one-pot copper-catalyzed oxidation with O2 in air as oxidant. The solvent mixture of acetonitrile and formamide (1:1) is optimized to ensure the oxidation of alcohols, deprotonation of phosphonium salt, and Wittig reaction occur efficiently in one pot. A broad range of substrates has been explored for this process, including three electron-withdrawing group (CO2Et, COPh, CN) functionalized phosphonium salts. They reacted not only with benzylic and heteroaromatic alcohols, but also with aliphatic alcohols, forming the corresponding α,β-unsaturated esters, ketones, and nitriles in moderate to excellent yields.
中文翻译:
由醇和Ph盐一锅法合成α,β-不饱和酯,酮和腈
摘要
通过在空气中以O 2为氧化剂的一锅铜催化氧化成功地实现了合成α,β-不饱和酯,酮和腈的通用方法。乙腈和甲酰胺(1:1)的溶剂混合物经过优化,可确保在一锅中有效地进行醇类的氧化,de盐的去质子化和Wittig反应。已针对该方法探索了广泛的底物,包括三个吸电子基团(CO 2 Et,COPh,CN)官能化的salts盐。它们不仅与苄基和杂芳族醇反应,而且与脂族醇反应,以中等至极好的收率形成相应的α,β-不饱和酯,酮和腈。
通过在空气中以O 2为氧化剂的一锅铜催化氧化成功地实现了合成α,β-不饱和酯,酮和腈的通用方法。乙腈和甲酰胺(1:1)的溶剂混合物经过优化,可确保在一锅中有效地进行醇类的氧化,de盐的去质子化和Wittig反应。已针对该方法探索了广泛的底物,包括三个吸电子基团(CO 2 Et,COPh,CN)官能化的salts盐。它们不仅与苄基和杂芳族醇反应,而且与脂族醇反应,以中等至极好的收率形成相应的α,β-不饱和酯,酮和腈。