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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 15, Number 12
BKCSDE 15(12)
December 20, 1994 

Synthesis of β,γ-Unsaturated Ketones through Ligand-Promoted Hydroiminoacylation of Dienes by Rh
Chul-Ho Jun*, Bon-Tak Koo, Jung-Bu Kang, Keun-Jae Kim
Chlorobis(isoprene)rhodium(Ⅰ) (3), prepared by olefin-exchange reaction of chlorobis(cyclooctene)rhodium dimer (2) with isoprene, reacted with benzaldimine 4 to give iminoacylrhodium(Ⅲ) η3-1,2-dimethylallyl complex 6. Ligand-promoted reductive elimination of 6 by pyridine and P(OMe)3 produced β,γ-unsaturated ketimine 8, which was readily hydrolyzed to give β,γ-unsaturated ketone 9. Other methyl branched dienes such as 2,3-dimethylbutadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-methyl-1,4-pentadiene and 2-methyl-1,4-pentadiene, were applied the synthesis of β,γ-unsaturated ketones. In case of 2,4-dimethyl-1,3-pentadiene, only γ,δ -unsaturated ketone 25, 1,2-addition product, was obtained, may be due to the mono-olefin coordination.
1064 - 1069
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