Neuhaus William C, Jemison Adriana L, Kozlowski Marisa C
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States.
ACS Catal. 2019 Dec 6;9(12):11067-11073. doi: 10.1021/acscatal.9b02608. Epub 2019 Oct 23.
The oxidative homocoupling of -alkenyl phenols and subsequent trapping of the resulting quinone methide with a variety of oxygen and nitrogen nucleophiles was achieved. Both β-β and β-O coupling isomers can be synthesized via either C-C coupling and two nucleophilic additions of one water molecule (β-β isomer) or C-O coupling followed by one nucleophilic addition of a water molecule (β-O isomer), respectively. Selectivity between these outcomes was achieved by leveraging understanding of the mechanism. Specifically, a qualitative predictive model for the selectivity of the coupling was formulated based on catalyst electronics, solvent polarity, and concentration.
实现了β-烯基酚的氧化均偶联反应以及随后生成的醌甲基化物与各种氧和氮亲核试剂的捕获。β-β和β-O偶联异构体均可分别通过C-C偶联和一个水分子的两次亲核加成反应（β-β异构体）或C-O偶联随后一个水分子的一次亲核加成反应（β-O异构体）来合成。通过对反应机理的理解实现了这些反应结果之间的选择性。具体而言，基于催化剂电子性质、溶剂极性和浓度建立了一个关于偶联选择性的定性预测模型。
