| 12358538 |
Kamijo S, Yamamoto Y: Synthesis of allyl cyanamides and N-cyanoindoles via the palladium-catalyzed three-component coupling reaction. J Am Chem Soc. 2002 Oct 9;124(40):11940-5.
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. |
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