Transition-Metal-Catalyzed Hydroamination of Olefins and Alkynes

Transition-Metal Catalyzed Hydroamination of Olefins and Alkynes... 

TRANSITION-METAL-CATALYZED HYDROAMINATION OF OLEFINS AND ALKYNES... 

TRANSITION-METAL-CATALYZED HYDROAMINATION OF OLEFINS AND ALKYNES Table 16.6. Effect of catalyst precursor on the intramolecular hydroamlnation In Equation 16.61. 

The hydroamination of olefins has been shown to occur by the sequence of oxidative addition, migratory insertion, and reductive elimination in only one case. Because amines are nucleophilic, pathways are available for the additions of amines to olefins and alkynes that are unavailable for the additions of HCN, silanes, and boranes. For example, hydroaminations catalyzed by late transition metals are thought to occur in many cases by nucleophilic attack on coordinated alkenes and alkynes or by nucleophilic attack on ir-allyl, iT-benzyl, or TT-arene complexes. Hydroaminations catalyzed by lanthanide and actinide complexes occur by insertion of an olefin into a metal-amide bond. Finally, hydroamination catalyzed by dP group 4 metals have been shown to occur through imido complexes. In this case, a [2+2] cycloaddition forms the C-N bond, and protonolysis of the resulting metallacycle releases the organic product. 

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