Control of ambident nucleophiles

亲核剂与亲电剂的加成是农用化学品和药物合成中的常见步骤。然而，使用两亲核试剂，例如在环丙康唑(一种真菌生长抑制剂)和甲氧西林(一种新的烟碱类杀虫剂)中，总是带来挑战，无论亲核试剂是简单的还是复杂的。选择性低于100%必然会降低工艺的经济性；必须分离或消除不需要的异构体--例如通过异构化--所有这些都需要时间和材料。这个项目将应用物理有机技术来阐明控制这种过程的区域选择性的基本机械方面，目标是通过机械开关产生二元控制，使用催化。

The addition of nucleophiles to electrophiles is a common step in the synthesis of agrochemical and pharmaceuticals. However, the use of ambident nucleophiles, as for example in cyproconazole (a fungal growth inhibitor) and thiamethoxam (a neonicotinoid insecticide), always presents a challenge, irrespective of whether the nucleophile is simple or complex. Selectivity less than 100%, by necessity, makes a process less economic; the unwanted isomer must be separated or eliminated - e.g., by isomerisation - all of which costs time and materials. This project will apply physical organic techniques to elucidate the fundamental mechanistic aspects that control the regioselectivity of such processes, with the goal of engendering binary control by mechanistic switch, using catalysis.