Bardagí Javier I, Rossi Roberto A
INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, Córdoba, Argentina.
J Org Chem. 2008 Jun 20;73(12):4491-5. doi: 10.1021/jo800358v. Epub 2008 May 20.
From the commercial 6-chloro-2,4-dimethoxypyrimidine (1) and by a photostimulated reaction with Me(3)Sn(-) ions, 2,4-dimethoxy-6-(trimethylstannyl)pyrimidine (2) was obtained in 95% yield. By the cross-coupling reaction of 2 with 1-iodonaphthalene as electrophile catalyzed by Pd (Stille reaction), 2,4-dimethoxy-6-(naphthalen-1-yl)pyrimidine (9) was obtained in 76% yield. By hydrolysis of 9, 6-(1-naphthyl)uracil was obtained in 98% of isolated yield. When the three steps (S(RN)1 reaction-cross coupling reaction-hydrolysis) were performed in a one-pot reaction, 6-substituted uracils (1-naphthyl, 4-chlorophenyl, 3-chlorophenyl, 2,3,4,5,6-pentafluorophenyl) were obtained (43-57%) of isolated pure products. When the electrophile was a benzoyl chloride, 6-benzoyl uracil (54%) and 6-(2-chlorobenzoyl) uracil (49%) were obtained in isolated pure products.
以市售的6-氯-2,4-二甲氧基嘧啶（1）为原料，通过与Me(3)Sn(-)离子进行光刺激反应，以95%的产率得到了2,4-二甲氧基-6-(三甲基锡基)嘧啶（2）。以2为原料，在Pd催化下与亲电试剂1-碘萘进行交叉偶联反应（Stille反应），以76%的产率得到了2,4-二甲氧基-6-(萘-1-基)嘧啶（9）。通过9的水解反应，以98%的分离产率得到了6-(1-萘基)尿嘧啶。当这三步反应（S(RN)1反应-交叉偶联反应-水解反应）在一锅反应中进行时，得到了6-取代尿嘧啶（1-萘基、4-氯苯基、3-氯苯基、2,3,4,5,6-五氟苯基）（分离得到的纯产物产率为43-57%）。当亲电试剂为苯甲酰氯时，则得到了6-苯甲酰基尿嘧啶（54%）和6-(2-氯苯甲酰基)尿嘧啶（49%）的分离纯产物。
