CH bond activation by rhodium(I) and the mechanism of the olefin isomerization: new synthesis of β,γ-unsaturated ketones via η1- or η3-alkylallylrhodium(III) complexes by reductive elimination

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Abstract

Acylrhodium(III)-η3-1-ethylallyl complex (7) was prepared by the reaction of 8-quinolinecarboxaldehyde (3) and 1,4-pentadienerhodium(I) chloride (2) by CH bond activation, followed by hydrometallation, and double bond migration. Higher concentrations of pyridine as coordinating ligand transforms η3-1-ethylallylrhodium(III) complexes (8a,8b) into η1-pent-2-enylrhodium(III) complex (11a). Acylrhodium(III)-η3-syn,anti-1,3-dimethylallyl complex (14) was also prepared from 1,3-pentadienerhodium(I) chloride (16) and 3. The reductive elimination of acylrhodium(III)-η1- and -η3-1-alkylallyl complexes by trimethylphosphite gives various β,γ-unsaturated ketones.

Original languageEnglish
Pages (from-to)361-370
Number of pages10
JournalJournal of Organometallic Chemistry
Volume390
Issue number3
DOIs
Publication statusPublished - 1990 Jul 10

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Rhodium
Alkenes
Isomerization
Ketones
rhodium
ketones
Pyridine
isomerization
alkenes
Olefins
Chlorides
elimination
Chemical activation
chlorides
Ligands
activation
methylidyne
synthesis
pyridines
ligands

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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title = "CH bond activation by rhodium(I) and the mechanism of the olefin isomerization: new synthesis of β,γ-unsaturated ketones via η1- or η3-alkylallylrhodium(III) complexes by reductive elimination",
abstract = "Acylrhodium(III)-η3-1-ethylallyl complex (7) was prepared by the reaction of 8-quinolinecarboxaldehyde (3) and 1,4-pentadienerhodium(I) chloride (2) by CH bond activation, followed by hydrometallation, and double bond migration. Higher concentrations of pyridine as coordinating ligand transforms η3-1-ethylallylrhodium(III) complexes (8a,8b) into η1-pent-2-enylrhodium(III) complex (11a). Acylrhodium(III)-η3-syn,anti-1,3-dimethylallyl complex (14) was also prepared from 1,3-pentadienerhodium(I) chloride (16) and 3. The reductive elimination of acylrhodium(III)-η1- and -η3-1-alkylallyl complexes by trimethylphosphite gives various β,γ-unsaturated ketones.",
author = "Chul-Ho Jun",
year = "1990",
month = "7",
day = "10",
doi = "10.1016/0022-328X(90)85104-7",
language = "English",
volume = "390",
pages = "361--370",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "3",

}

TY - JOUR

T1 - CH bond activation by rhodium(I) and the mechanism of the olefin isomerization

T2 - new synthesis of β,γ-unsaturated ketones via η1- or η3-alkylallylrhodium(III) complexes by reductive elimination

AU - Jun, Chul-Ho

PY - 1990/7/10

Y1 - 1990/7/10

N2 - Acylrhodium(III)-η3-1-ethylallyl complex (7) was prepared by the reaction of 8-quinolinecarboxaldehyde (3) and 1,4-pentadienerhodium(I) chloride (2) by CH bond activation, followed by hydrometallation, and double bond migration. Higher concentrations of pyridine as coordinating ligand transforms η3-1-ethylallylrhodium(III) complexes (8a,8b) into η1-pent-2-enylrhodium(III) complex (11a). Acylrhodium(III)-η3-syn,anti-1,3-dimethylallyl complex (14) was also prepared from 1,3-pentadienerhodium(I) chloride (16) and 3. The reductive elimination of acylrhodium(III)-η1- and -η3-1-alkylallyl complexes by trimethylphosphite gives various β,γ-unsaturated ketones.

AB - Acylrhodium(III)-η3-1-ethylallyl complex (7) was prepared by the reaction of 8-quinolinecarboxaldehyde (3) and 1,4-pentadienerhodium(I) chloride (2) by CH bond activation, followed by hydrometallation, and double bond migration. Higher concentrations of pyridine as coordinating ligand transforms η3-1-ethylallylrhodium(III) complexes (8a,8b) into η1-pent-2-enylrhodium(III) complex (11a). Acylrhodium(III)-η3-syn,anti-1,3-dimethylallyl complex (14) was also prepared from 1,3-pentadienerhodium(I) chloride (16) and 3. The reductive elimination of acylrhodium(III)-η1- and -η3-1-alkylallyl complexes by trimethylphosphite gives various β,γ-unsaturated ketones.

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

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