Synthesis of allyl cyanamides and N-cyanoindoles via the palladium-catalyzed three-component coupling reaction.
Synthesis of allyl cyanamides and N-cyanoindoles via the palladium-catalyzed three-component coupling reaction.
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DOI：
10.1002/chin.200309048
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发表时间：
2002-09
影响因子：
15
通讯作者：
S. Kamijo;Yoshinori Yamamoto
中科院分区：
文献类型：
--
作者：
S. Kamijo;Yoshinori Yamamoto
在Pd（2）（dba）（3）·CHCl（3）（2.5mol%）和dppe（1，2-双（二苯基膦基）乙烷）（10mol%）存在下，进行了钯催化的芳基异腈、烯丙基甲基碳酸酯和叠氮三甲基硅的三组分偶联反应（TCCR）。以优异的产率得到了具有多种官能团的烯丙基芳基氰胺。这种钯催化的TCCR被进一步用于N-氰基吲哚的合成。在Pd（2）（dba）（3）、CHCl（3）（2.5mol%）和三（2-呋喃基）膦（10mol%）存在下，2-炔基异氰基苯、烯丙基甲基碳酸酯和三甲基硅基叠氮在较高温度下反应，得到N-氰基吲哚。（η（3）-烯丙基）（η（3）-氰氨基）钯配合物是双-π-烯丙基钯配合物的类似物，是TCCR中的关键中间体，并且涉及Curtius重排的π-烯丙基钯模拟物以产生（η（3）-烯丙基）（η（3）-氰氨基）钯中间体。
The palladium-catalyzed three-component coupling reaction (TCCR) of aryl isocyanides, allyl methyl carbonate, and trimethylsilyl azide was conducted in the presence of Pd(2)(dba)(3).CHCl(3) (2.5 mol %) and dppe (1,2-bis(diphenylphosphino)ethane) (10 mol %). Allyl aryl cyanamides with a wide variety of functional groups were obtained in excellent yields. This palladium-catalyzed TCCR was further utilized for the synthesis of N-cyanoindoles. The reaction of 2-alkynylisocyanobenzenes, allyl methyl carbonate, and trimethylsilyl azide in the presence of Pd(2)(dba)(3).CHCl(3) (2.5 mol %) and tri(2-furyl)phosphine (10 mol %) at higher temperatures afforded N-cyanoindoles in good to allowable yields. (eta(3)-Allyl)(eta(3)-cyanamido)palladium complex, an analogue of the bis-pi-allylpalladium complex, is a key intermediate in the TCCR, and a pi-allylpalladium mimic of the Curtius rearrangement is involved to generate the (eta(3)-allyl)(eta(3)-cyanamido)palladium intermediate.