Allyl aryl cyanamide

Palladium-mediated cydization based on the reactivity of o-alkynyl or alkenyl-phenyl isonitriles have been developed [105]. On the basis of their earlier studies on the three-component synthesis of allyl aryl cyanamides [106], Yamamoto and co-workers reported a palladium-catalyzed three-component coupling reaction of 2-alkynylisocyanobenzenes 122 with allyl methyl carbonate and trimethylsilylazide leading to N-cyanoindoles 125 [107]. One of the key steps of the proposed mechanism is the formation of 7i-allylpalladium carbodiimide 123 and its isomerization to rc-allylpalladium cyanamide complex 124 (Scheme 8.50). 

Tertiary amines are cleaved with BrCN to give an alkyl bromide and a disubstituted cyanamide (Scheme 21). This process is called the von Braun reaction. Many examples have been reviewed. Tertiary amines with different R groups cleave so that the most reactive alkyl bromide is formed. Benzyl and allyl cleave better than alkyl, lower alkyl cleaves better than higher alkyl and aryl is not cleaved at... 

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