Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago 6094411, Chile.
J Org Chem. 2009 Aug 21;74(16):6374-7. doi: 10.1021/jo901137f.
The Brønsted plots for the title reactions are linear with slopes of 0.53-0.56. The magnitude of the slopes and the fact that there are no breaks at the predicted pK(a) for stepwise mechanisms indicate that these reactions are concerted. This finding is in great contrast to the stepwise mechanisms found for the pyridinolysis of other carbonates. The concerted mechanism is attributed to the fact that the title carbonates possess two O-aryl groups, one of them being an exceptionally good nucleofuge.
标题反应的布朗斯台德图呈线性，斜率为 0.53-0.56。斜率的大小以及逐步机制预测的 pK(a) 处没有断点的事实表明，这些反应是协同的。这一发现与其他碳酸盐的吡啶解反应中发现的逐步机制形成了鲜明的对比。协同机制归因于标题碳酸盐具有两个 O-芳基基团，其中一个是非常好的亲核试剂。
