Ruthenium catalysis rearrangements

New amine functionalization reactions have been applied to the functionalization of benzodiazepines, for example, twofold methylation of 2,3,4,5-tetrahydro-lff-benzo[e][l,4]diazepine was achieved using carbon dioxide and phenylsilane with ruthenium catalysis (13AGE9568). A range of readily available 3,4-dihydro-lH-benzo[e][l,4]diazepine-2,5-diones underwent iV-acylation followed by a dehydrative ring-contraction rearrangement process to afford the corresponding oxazoloquinolinones (13OL1052). 

Acrylic acid formation, 61 Activation catalysis, 28 Activation energies, 112 Activation energy barrier electronic rearrangements, 99 Michaelis complex formation, 95 reduction of ruthenium, 173 Activation of CO, 131/ Activation parameters, 31... 

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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