Department of Chemistry, The University of Texas at San Antonio, San Antonio, Texas 78249, United States.
J Org Chem. 2020 Mar 6;85(5):3728-3741. doi: 10.1021/acs.joc.9b03346. Epub 2020 Feb 5.
Oxidative cleavage reactions of arylalkenes by -butyl hydroperoxide that occur by free radical processes provide access to carboxylic acid or ketone products. However, the pathway to these cleavage products is complex, initiated by regioselective oxygen radical addition to the carbon-carbon double bond. Subsequent reactions of the initially formed benzyl radical lead eventually to carbon-carbon cleavage. Thorough investigations of these reactions have identified numerous reaction intermediates that are on the pathways to final product formation, and they have identified a new synthetic methodology for the synthesis of peroxy radical addition-induced hydroperoxide formation.
过氧叔丁烷引发的芳基烯烃的氧化断裂反应是自由基过程，可得到羧酸或酮类产物。
然而，这些断裂产物的途径是复杂的，由碳-碳双键的区域选择性氧自由基加成引发。
最初形成的苄基自由基的后续反应最终导致碳-碳键的断裂。
对这些反应的深入研究已经确定了许多处于最终产物形成途径中的反应中间体，并为过氧自由基加成诱导的过氧化物形成的合成方法学提供了新的见解。
