Ru-3(CO)(12)-catalyzed coupling reaction of sp(3) C-H bonds adjacent to a nitrogen atom in alkylamines with alkenes

Catalytic reactions which involve the cleavage of an sp(3) C-H bond adjacen t to a nitrogen atom in N-2-pyridynyl alkylamines are described. The use of Ru-3(CO)(12) as the catalyst results in the addition of the sp(3) C-H bond across the alkene bond to give the coupling products. A variety of alkenes , including terminal, internal, and cyclic alkenes, can be used for the cou pling reaction. The presence of directing groups, such as pyridine, pyrimid ine, and an oxazoline ring, on the nitrogen of the amine is critical for a successful reaction. This result indicates the importance of the coordinati on of the nitrogen atom to the ruthenium catalyst. In addition, the nature of the substituents. on the pyridine ring has a significant effect on the e fficiency of the reaction. Thus, the substitution of an electron-withdrawin g group on the pyridine ring as well as a substitution adjacent to the sp(2 ) nitrogen in the pyridine ring dramatically retards the reaction. Cyclic a mines are more reactive than acyclic ones. The choice of solvent is also ve ry important. Of the solvents examined, 2-propanol is the solvent of choice .