Palladium catalysis diamination

Palladium catalysis can also be used for the introduction of nitrogen substituents, e.g., Scheme 161 <2004TL769>. 3-Bromothiophene can be coupled with 2-pyridone to form the A-(3-thienyl) derivative using a catalyst consisting of Cul in the presence of N,A-dimethylcyclohexane-1,2-diamine and KOAc or K2C03 <2005T2931>. 

In 2003, O Shaughnessy and Scott reported the first example of rare-earth metal complexes supported by biaryl diamide ligands as the catalysts for the hydroamination reactions [159]. A series of C2 symmetric secondary diamine proligands L37-L40 were prepared by arylations of (7 )-2,2 -diamino-6,6 -dimethybiphenyl under palladium catalysis. L37 reacted with complexes [Ln N(SiHMe2)2 3(THF)2] to form the biaryl diamide complexes [Ln(L37) N(SiHMe2)2 (THF)2] (Ln = Y (190), La (191), Sm (192)). Deprotonation... 

Recently, the Heck reaction was extended to carbonvlation of aromatic dibromides with aromatic diamines in the presence of carbon monoxide. High molecular weight aromatic polyamides form with the help of palladium catalysis ... 

Cyclic secondary amines are also produced by the ring expansion of O-sulphonyloximes via a Beckmann rearrangement/ the cyclization of a,aliphatic diamines by a ruthenium catalyst/ the palladium-promoted ring closure of amino-alkenes/ and the sulphonamidomercuration of 1,4- and 1,5-dienes. The latter two reactions form part of a wealth of new literature on the amination of olefins and acetylenes via aminomercuration " and via palladium catalysis. ... 

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