Ruthenium-catalyzed intermolecular coupling reactions of arylamines with ethylene and 1,3-dienes: mechanistic insight on hydroamination vs ortho-C-H bond activation

[reaction: see text]. The cationic ruthenium complex [(PCy3)2(CO)(Cl)Ru=CHCH=C(CH3)2]+BF4- was found to be an effective catalyst for the coupling reaction of aniline and ethylene to form a approximately 1:1 ratio of N-ethylaniline and 2-methylquinoline products. The analogous reaction with 1,3-diene...

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Bibliographic Details
Published in:Organic letters 2005-05, Vol.7 (11), p.2181-2183
Main Authors: Yi, Chae S, Yun, Sang Young
Format: Article
Language:English
Subjects:
Alkadienes - chemistry
Amines - chemistry
Aniline Compounds - chemical synthesis
Aniline Compounds - chemistry
Catalysis
Ethylenes - chemistry
Isotopes - pharmacokinetics
Quinolines - chemical synthesis
Ruthenium - chemistry
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Summary:[reaction: see text]. The cationic ruthenium complex [(PCy3)2(CO)(Cl)Ru=CHCH=C(CH3)2]+BF4- was found to be an effective catalyst for the coupling reaction of aniline and ethylene to form a approximately 1:1 ratio of N-ethylaniline and 2-methylquinoline products. The analogous reaction with 1,3-dienes resulted in the preferential formation of Markovnikov addition products. The normal isotope effect of k(NH)/k(ND) = 2.2 (aniline and aniline-d7 at 80 degrees C) and the Hammett rho = -0.43 (correlation of para-substituted p-X-C6H4NH2) suggest an N-H bond activation rate-limiting step for the catalytic reaction.
ISSN:1523-7060
DOI:10.1021/ol050524+