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 language | English |
|---|---|
| Pages (from-to) | 10935-10941 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 123 |
| Issue number | 44 |
| DOIs | |
| Publication status | Published - 2001 Nov 7 |
| Externally published | Yes |
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- Chemistry(all)
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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 journal › Article
}
TY - JOUR
T1 - Ru3(CO)12-catalyzed coupling reaction of sp3 C - H bonds adjacent to a nitrogen atom in alkylamines with alkenes
AU - Chatani, N.
AU - Asaumi, T.
AU - Yorimitsu, S.
AU - Ikeda, T.
AU - Kakiuchi, Fumitoshi
AU - Murai, S.
PY - 2001/11/7
Y1 - 2001/11/7
N2 - 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.
AB - 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.
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U2 - 10.1021/ja011540e
DO - 10.1021/ja011540e
M3 - Article
VL - 123
SP - 10935
EP - 10941
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 44
ER -