Niederer Kyle A, Gilmartin Philip H, Kozlowski Marisa C
Department of Chemistry, Roy and Diana Vagelos Laboratories, University of Pennsylvania, Philadelphia, Pennsylvania 19014, United States.
ACS Catal. 2020 Dec 18;10(24):14615-14623. doi: 10.1021/acscatal.0c04515. Epub 2020 Nov 25.
The oxidative photocatalytic method for phenol-phenol homo-coupling and cross-coupling is described and isolated yields of 16-97% are obtained. Measured oxidation potentials and computed nucleophilicity parameters support a mechanism of nucleophilic attack of one partner onto the oxidized neutral radical form of the other partner. Understanding of this model permitted development of cross-coupling reactions between nucleophilic phenols/arenes and easily oxidized phenols with high selectivity and efficiency. A highlight of this method is that one equivalent of each coupling partner is utilized. Building on these findings, a non-enzymatic, catalytic method for coupling tyrosine was also developed.
描述了用于苯酚-苯酚均偶联和交叉偶联的氧化光催化方法,并获得了16%-97%的分离产率。测得的氧化电位和计算出的亲核性参数支持一种亲核试剂攻击另一种亲核试剂氧化中性自由基形式的机理。对该模型的理解有助于开发亲核酚/芳烃与易氧化酚之间具有高选择性和高效率的交叉偶联反应。该方法的一个亮点是每种偶联试剂仅使用一当量。基于这些发现,还开发了一种用于酪氨酸偶联的非酶催化方法。