Ruthenium complexes cyanates

An important application of oxidation of a C-H bond adjacent to a nitrogen atom is the selective oxidation of amides. This reaction proceeds in the presence of ferf-BuOOH as the oxidant and Ru(II) salts. Thus in the example of Eq. (36), the a-tert-butylperoxy amide of the isoquinoline was obtained, which is an important synthetic intermediate for natural products [138]. This product can be conveniently reacted with a nucleophile in the presence of a Lewis add. Direct trapping of the iminium ion complex by a nudeophile was achieved in the presence of trimethylsilyl cyanide, giving a-cyanated amines as shown in Eq. (37) [45]. This ruthenium/peracid oxidation reaction provides an alternative to the Strecker reaction for the synthesis of a-amino acid derivatives since they involve the same a-cyano amine intermediates. In this way N-methyl-N-(p-methoxyphenyl) glycine could be prepared from N,N-dimethyl-p-methoxyaniline in 82% yield. 

Cobaltaie(l -), dodecacarbonylirontri-, tetraethylammonium, 27 188 Cobaltate(l -), dodecacarbonylirontri-, (triphenylphosphine)gold(l -(-), 27 188 -------, dodecacarbonylrutheniumtri-, tetraethylammonium, 26 358 Copper, (acetonitrile)dodecacarbonyltrico-balt ruthenium-, 26 359 Crystal growth, 26 377 Cyanate, tungsten complex, 26 42 Cycloheptatriene, molybdenum complex, 27 4... 

While the majority of transition metal photocatalysts are based upon ruthenium and iridium complexes, similar intermolecular cyanation reactions can also be accomplished using gold-based transition metal photocatalysts. 

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