Tetrabutylammonium Iodide Catalyzed Synthesis Of Benzyl Ester And Allylic Ester

Recently, all kinds of oxidative coupling reactions have obtained exciting interest under TBHP/TBAI system in organic synthesis. In comparison with tradition metal-catalyzed coupling reactions, it is not require expensive metal. In contrast, it uses commercially available and inexpensive tetrabutylammonium iodide (TBAI) as a catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant which accords with the development of green chemistry.This thesis composes with two parts as follows:1. Tetrabutylammonium Iodide Catalyzed Synthesis of Benzyl Ester with Tert-Butyl Hydroperoxide as an OxidantWe developed a new method for the construction of benzyl esters which formed from various carboxylic acids and alkylbenzenes under metal-free system. In the system, tetrabutylammonium iodide is catalyst, tert-butyl hydroperoxide is oxidant and H2O is solvent, under the condition, carboxylic acid and alkyl benzene generates the acyloxy radical and benzyl radical, respectively. Finally, the coupling of acyloxy radical and benzyl radical forms the desired benzyl ester.The system has the following advantages:(1) It accords with the development of green chemistry by using tert-butyl hydroperoxide (TBHP) as the oxidant and H2O as solvent;(2) A wide range of commercially available carboxylic acids as starting materials;(3) Mild reaction conditions, simple operation and carried out directly in the air.2. Tetrabutylammonium Iodide Catalyzed Synthesis of Allylic Ester with Tert-Butyl Hydroperoxide as an OxidantWe report a novel method for the synthesis of allylic ester under metal-free system. Under the system, using tert-butyl hydroperoxide as oxidant, tetrabutylammonium iodide as catalyst and benzene as solvent to provide both the acyloxy radical and allylic radical, respectively. Then the coupling of acyloxy radical and allylic radical forms the desired allylic ester.The system has the following advantages:(1) A new allylic ester synthesis was developed via metal-free condition, easily available starting materials, high atom economy;(2) Mild reaction conditions, operational simplicity and carried out directly in the air;(3) A wide range of carboxylic acids and alkenes and good tolerance with diverse functional groups.