Oxidative coupling of ketone enolates by ferric chloride

Thermochemical Considerations of Metal Enolates

“…As was discussed in Section VI for the reactions of enolates with the oxidizing cation Cu(II), Fe(III) also oxidizes enolates to form products associated with formal radical dimerization 232 . The presumed intermediate enoxyl radicals react with FeCl 3 , not by formation of Fe(IV) enolates 233 , but rather from an α-chlorinated ketone product + FeCl 2 , thereby providing a thermochemical upper bound for the enthalpy of formation of these haloketones.…”

The case for noncompetitive cyclizative options during attempted expedient construction of the core ring system of CP-263,114

“…The ability of cupric and ferric ions to bring about the oxidative coupling of ester enolates, recognized more than 20 years ago, 21 has serviced several synthetic objectives in both its intermolecular [22][23][24] and intramolecular variants. 25,26 Comparable success has been realized with elemental iodine as the oxidant.…”

Diastereoselective Construction of All-Carbon Quaternary Stereocenters via Intramolecular Oxidative Cross-Coupling Reaction

“…为了证明所发展的双烯醇硅醚化合物分子内交叉 氧化偶联反应对于控制反应非对映选择性的必要性, 我 们接着进行了分子间交叉氧化偶联反应作为对照实验. 根据 Frazier 和 Harlow [21] [8,9] , 我们 提出了该反应可能的机理(Scheme 6). 首先, 在 CAN 存 在的条件下, 双烯醇硅醚底物 14 通过单电子转移过程 (SET)生成自由基中间体 II [22] .…”