Department of Chemistry and Biochemistry, Florida State University, 95 Chieftan Way, Tallahassee, FL 32306, USA.
Chem Commun (Camb). 2021 Mar 11;57(21):2693-2696. doi: 10.1039/d1cc00056j.
Disclosed in this communication is a thorough study on the dearomative addition of organomagnesium nucleophiles to N-alkyl pyridinium electrophiles. The regiochemical outcomes have observable and predictable trends associated with the substituent patterns on the pyridinium electrophile. Often, the substituent effects can be either additive, giving high selectivities, or ablative, giving competing outcomes. Additionally, the nature of the organometallic nucleophilic component was also investigated for its role in the regioselective outcome. The effects of either reactive component are important to both the overall reactivity and site of nucleophilic addition. The utility of these observed trends is demonstrated in a concise, dearomative synthesis of a tricyclic compound shown to have insecticidal activity.
本通讯披露了对 N-烷基吡啶鎓亲电试剂的有机镁亲核试剂的去芳构化加成的深入研究。区域化学结果与吡啶鎓亲电试剂上的取代模式具有可观察和可预测的趋势。通常，取代基效应可以是加合的，给出高选择性，或者是消除的，给出竞争的结果。此外，还研究了有机金属亲核性组分的性质，以了解其在区域选择性结果中的作用。两种反应性组分的影响对于整体反应性和亲核加成的位置都很重要。这些观察到的趋势的实用性在一个简洁的、去芳构化的三环化合物的合成中得到了证明，该化合物显示出杀虫活性。
