Patil Nitin T, Wu Huanyou, Kadota Isao, Yamamoto Yoshinori
Department of Chemistry and Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
J Org Chem. 2004 Dec 10;69(25):8745-50. doi: 10.1021/jo0485684.
The allylation of aromatic amines with alkynes proceeded smoothly in the presence of catalytic amounts of Pd(PPh(3))(4) and benzoic acid. The allylation products were obtained in high yields in a regio- and stereoselective manner. The effect of various groups on the nitrogen atom of anilines was studied. Regardless of the substituent (electron withdrawing or electron donating) on the aromatic ring, the reaction proceeded well. Various functionalities, including -CH(3), -OMe, -Cl, -CN, -COOMe, -NO(2) and -COCH(3) were tolerated under the reaction conditions. Similarly, the allylation of alpha-aryl aldehydes proceeded well with the same level of regio- and stereoselectivity as the allylation of aromatic amines. This reaction provides the second example of the transition metal catalyzed direct alpha-allylation of aldehydes.
在催化量的Pd(PPh(3))(4)和苯甲酸存在下，芳香胺与炔烃的烯丙基化反应顺利进行。烯丙基化产物以区域和立体选择性的方式高产率得到。研究了各种基团对苯胺氮原子的影响。无论芳环上的取代基是吸电子还是供电子，反应都能顺利进行。在反应条件下，包括-CH(3)、-OMe、-Cl、-CN、-COOMe、-NO(2)和-COCH(3)在内的各种官能团都能耐受。同样，α-芳基醛的烯丙基化反应也能顺利进行，其区域和立体选择性与芳香胺的烯丙基化反应相同。该反应提供了过渡金属催化醛直接α-烯丙基化的第二个例子。
