无金属催化烯烃反马氏氧化为酯类化合物研究

Study on metal-free catalytic anti-markovian oxidation ofalkenes to ester compounds

烯烃的化学转化一直是新物质创造科学研究的前沿和核心,其中烯烃的氧化官能团化在合成化学中具有重要的研究意义和应用价值.以烯烃为原料,通过筛查不同的碘源、反应温度、溶剂、反应时间等因素,探究烯烃在Oxone条件下高选择性反马氏氧化为酯类化合物.该催化体系对含有吸电子或者给电子基团取代的烯烃都很良好的适用性.通过对照实验探究了反应可能的机理,即反应通过串联碘官能团化/芳基迁移,经由醛、羧酸中间体进而转化为酯类产物.

Chemical transformation of alkenes has always been the frontier and core of scientific research on the creation of new substances.The oxidative functionalization of C=C bonds in alkenes has occupied a central place in organic synthesis with important implications in industry.Herein,we disclose an efficient protocol for the direct formation of ester compounds by anti-Markovnikov selective oxidation cleavage of C=C bonds in alkenes using ammonium iodide as an iodine source and Oxone as an oxidant.This transformation proceeds smoothly at ambient temperature and tolerates the various functional groups to provide the corresponding esters in moderate to high yields.Control experiments revealed that the reaction proceeds via aldehyde and carboxylic acid intermediates through the tandem iodofunctionalization/aryl migration.