Mosrin Marc, Knochel Paul
Ludwig-Maximilians Universität München, Department Chemie & Biochemie, Butenandtstrasse 5-13, Haus F, 81377 München, Germany.
Chemistry. 2009;15(6):1468-77. doi: 10.1002/chem.200801831.
Efficient zincation and magnesiation of chlorinated pyrimidines can be performed at convenient temperatures (e.g., 25 and 55 degrees C) by using TMPMgCl x LiCl and TMP(2)Zn x 2 MgCl(2) x 2 LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) as effective bases. Quenching of the resulting zincated or magnesiated pyrimidines with various electrophiles furnishes highly functionalized pyrimidines in 51-93% yield. Oxidative aminations were carried out, thus leading to aminated pyrimidines. By using this methodology, we have also prepared pharmaceutically relevant pyrazolopyrimidines and the fungicide Mepanipyrim.
通过使用TMPMgCl·LiCl和TMP₂Zn·2MgCl₂·2LiCl（TMP = 2,2,6,6 - 四甲基哌啶基）作为有效的碱，可以在适宜的温度（例如25和55摄氏度）下对氯化嘧啶进行高效的锌化和镁化反应。用各种亲电试剂淬灭所得的锌化或镁化嘧啶，可得到产率为51 - 93%的高度官能化嘧啶。进行了氧化胺化反应，从而得到胺化嘧啶。通过使用这种方法，我们还制备了与药物相关的吡唑并嘧啶和杀菌剂嘧菌胺。
