Transition Metal-Catalyzed Intramolecular Cyclization of 1,5- And 1,6-Dienes via Direct Cleavage and Addition of the Carbon-Hydrogen Bond

Naoaki Fujii, Fumitoshi Kakiuchi, Airi Yamada, Naoto Chatani, Shinji Murai

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73 Citations (Scopus)

Abstract

Ruthenium- and rhodium-catalyzed intramolecular C-H/olefin coupling reactions of 1-(2-pyridyl)-, 1-(2-imidazolyl-, and 1-(2-oxazolyl)-1,5-dienes proceeded in a regiospecific manner to give 5-membered ring products. Their 1,6-diene analogues are also applicable to the cyclization reaction to give the corresponding 5- and 6-membered carbocycles. For the cyclization of the pyridine derivatives, [RhCl(PPh3)3] showed the highest catalytic activity with respect to efficiency and selectivity. When the imidazole derivatives were employed to the cyclization reaction, the combination of the rhodium(I) complex and the relatively sterically bulky phosphine (e.g., PCy3 and PPFOMe) was a quite effective catalyst system. In the case of the oxazoles, the ruthenium complex, [Ru(H)2(CO)(PPh3)3], showed the highest activity among the catalysts examined. These catalytic reactions usually proceed at 120°C. The [RhCl(PPh3)3]-catalyzed cyclization reaction of 2-[(1E)-4,4-dimethyl-1,5-hexadienyl]pyridine smoothly proceeded even at room temperature to give the corresponding cyclized product in 93% yield after 24 h. A hybrid catalyst system containing the rhodium(I) and both PPh3 and P(o-tolyl)3 had a slightly better catalytic activity compared with that of [RhCl(PPh3)3]. The intramolecular cyclization can be also applied to the C-H/CO/olefin coupling reactions. These carbonylation reactions gave the 5-membered ring ketones exclusively. The intramolecular C-H/olefin coupling reactions provide a new entry for constructing carbocyclic compounds from 1,n-dienes.

Original languageEnglish
Pages (from-to)285-298
Number of pages14
JournalBulletin of the Chemical Society of Japan
Volume71
Issue number1
Publication statusPublished - 1998 Jan
Externally publishedYes

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Cyclization
Transition metals
Hydrogen bonds
Carbon
Rhodium
Alkenes
phosphine
Ruthenium
Carbon Monoxide
Catalysts
Catalyst activity
Oxazoles
Derivatives
Carbonylation
Catalyst selectivity
Ketones
chlorotris(triphenylphosphine)rhodium
Temperature
pyridine

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Transition Metal-Catalyzed Intramolecular Cyclization of 1,5- And 1,6-Dienes via Direct Cleavage and Addition of the Carbon-Hydrogen Bond. / Fujii, Naoaki; Kakiuchi, Fumitoshi; Yamada, Airi; Chatani, Naoto; Murai, Shinji.

In: Bulletin of the Chemical Society of Japan, Vol. 71, No. 1, 01.1998, p. 285-298.

Research output: Contribution to journalArticle

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abstract = "Ruthenium- and rhodium-catalyzed intramolecular C-H/olefin coupling reactions of 1-(2-pyridyl)-, 1-(2-imidazolyl-, and 1-(2-oxazolyl)-1,5-dienes proceeded in a regiospecific manner to give 5-membered ring products. Their 1,6-diene analogues are also applicable to the cyclization reaction to give the corresponding 5- and 6-membered carbocycles. For the cyclization of the pyridine derivatives, [RhCl(PPh3)3] showed the highest catalytic activity with respect to efficiency and selectivity. When the imidazole derivatives were employed to the cyclization reaction, the combination of the rhodium(I) complex and the relatively sterically bulky phosphine (e.g., PCy3 and PPFOMe) was a quite effective catalyst system. In the case of the oxazoles, the ruthenium complex, [Ru(H)2(CO)(PPh3)3], showed the highest activity among the catalysts examined. These catalytic reactions usually proceed at 120°C. The [RhCl(PPh3)3]-catalyzed cyclization reaction of 2-[(1E)-4,4-dimethyl-1,5-hexadienyl]pyridine smoothly proceeded even at room temperature to give the corresponding cyclized product in 93{\%} yield after 24 h. A hybrid catalyst system containing the rhodium(I) and both PPh3 and P(o-tolyl)3 had a slightly better catalytic activity compared with that of [RhCl(PPh3)3]. The intramolecular cyclization can be also applied to the C-H/CO/olefin coupling reactions. These carbonylation reactions gave the 5-membered ring ketones exclusively. The intramolecular C-H/olefin coupling reactions provide a new entry for constructing carbocyclic compounds from 1,n-dienes.",
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