Ru3(CO)12-catalyzed coupling reaction of sp3 C - H bonds adjacent to a nitrogen atom in alkylamines with alkenes

N. Chatani, T. Asaumi, S. Yorimitsu, T. Ikeda, Fumitoshi Kakiuchi, S. Murai

Research output: Contribution to journalArticle

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Abstract

Catalytic reactions which involve the cleavage of an sp3 C-H bond adjacent to a nitrogen atom in N-2-pyridynyl alkylamines are described. The use of Ru3(CO)12 as the catalyst results in the addition of the sp3 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 coupling reaction. The presence of directing groups, such as pyridine, pyrimidine, and an oxazoline ring, on the nitrogen of the amine is critical for a successful reaction. This result indicates the importance of the coordination 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 efficiency of the reaction. Thus, the substitution of an electron-withdrawing group on the pyridine ring as well as a substitution adjacent to the sp2 nitrogen in the pyridine ring dramatically retards the reaction. Cyclic amines are more reactive than acyclic ones. The choice of solvent is also very important. Of the solvents examined, 2-propanol is the solvent of choice.

Original languageEnglish
Pages (from-to)10935-10941
Number of pages7
JournalJournal of the American Chemical Society
Volume123
Issue number44
DOIs
Publication statusPublished - 2001 Nov 7
Externally publishedYes

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Alkenes
Carbon Monoxide
Pyridine
Olefins
Nitrogen
Atoms
Amines
Substitution reactions
Cycloparaffins
Catalysts
Ruthenium
2-Propanol
Propanol
Electrons
pyridine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Ru3(CO)12-catalyzed coupling reaction of sp3 C - H bonds adjacent to a nitrogen atom in alkylamines with alkenes. / Chatani, N.; Asaumi, T.; Yorimitsu, S.; Ikeda, T.; Kakiuchi, Fumitoshi; Murai, S.

In: Journal of the American Chemical Society, Vol. 123, No. 44, 07.11.2001, p. 10935-10941.

Research output: Contribution to journalArticle

Chatani, N. ; Asaumi, T. ; Yorimitsu, S. ; Ikeda, T. ; Kakiuchi, Fumitoshi ; Murai, S. / Ru3(CO)12-catalyzed coupling reaction of sp3 C - H bonds adjacent to a nitrogen atom in alkylamines with alkenes. In: Journal of the American Chemical Society. 2001 ; Vol. 123, No. 44. pp. 10935-10941.
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AU - Kakiuchi, Fumitoshi

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