Substituent effects on stoichiometric and catalytic cleavage of carbon-nitrogen bonds in aniline derivatives by ruthenium-phosphine complexes

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Abstract

The reactivity of various o-acylaniline derivatives with ruthenium complexes was examined. The reaction of o-acylanilines with RuH 2(CO)(PPh3)3 (1) or an activated ruthenium species formulated as "Ru(CO)(PPh3)3" (4) gave amido hydrido complexes 3 and aryl amido complexes 6 formed via N-H and C-N bond cleavage, respectively. Addition of olefins, such as vinylsilanes, accelerates the C-N bond cleavage. The aryl amido complexes 6 can provide the C-N arylation product upon treatment with arylboronates. The relative reactivity of o-acylanilines bearing various substituents was investigated by competition experiments, and it was found that electron-donating substituents increase the relative facileness of the C-N bond cleavage in both stoichiometric and catalytic reactions. The trend observed here is different from the one observed for the previously reported tantalum-mediated C-N bond cleavage.

Original languageEnglish
Pages (from-to)682-690
Number of pages9
JournalOrganometallics
Volume32
Issue number2
DOIs
Publication statusPublished - 2013 Jan 28

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phosphine
Ruthenium
Carbon Monoxide
aniline
phosphines
ruthenium
cleavage
Bearings (structural)
Nitrogen
Carbon
Tantalum
Derivatives
nitrogen
carbon
Alkenes
reactivity
Electrons
tantalum
alkenes
Experiments

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Substituent effects on stoichiometric and catalytic cleavage of carbon-nitrogen bonds in aniline derivatives by ruthenium-phosphine complexes",
abstract = "The reactivity of various o-acylaniline derivatives with ruthenium complexes was examined. The reaction of o-acylanilines with RuH 2(CO)(PPh3)3 (1) or an activated ruthenium species formulated as {"}Ru(CO)(PPh3)3{"} (4) gave amido hydrido complexes 3 and aryl amido complexes 6 formed via N-H and C-N bond cleavage, respectively. Addition of olefins, such as vinylsilanes, accelerates the C-N bond cleavage. The aryl amido complexes 6 can provide the C-N arylation product upon treatment with arylboronates. The relative reactivity of o-acylanilines bearing various substituents was investigated by competition experiments, and it was found that electron-donating substituents increase the relative facileness of the C-N bond cleavage in both stoichiometric and catalytic reactions. The trend observed here is different from the one observed for the previously reported tantalum-mediated C-N bond cleavage.",
author = "Tetsuro Koreeda and Takuya Kochi and Fumitoshi Kakiuchi",
year = "2013",
month = "1",
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doi = "10.1021/om3011855",
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journal = "Organometallics",
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publisher = "American Chemical Society",
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T1 - Substituent effects on stoichiometric and catalytic cleavage of carbon-nitrogen bonds in aniline derivatives by ruthenium-phosphine complexes

AU - Koreeda, Tetsuro

AU - Kochi, Takuya

AU - Kakiuchi, Fumitoshi

PY - 2013/1/28

Y1 - 2013/1/28

N2 - The reactivity of various o-acylaniline derivatives with ruthenium complexes was examined. The reaction of o-acylanilines with RuH 2(CO)(PPh3)3 (1) or an activated ruthenium species formulated as "Ru(CO)(PPh3)3" (4) gave amido hydrido complexes 3 and aryl amido complexes 6 formed via N-H and C-N bond cleavage, respectively. Addition of olefins, such as vinylsilanes, accelerates the C-N bond cleavage. The aryl amido complexes 6 can provide the C-N arylation product upon treatment with arylboronates. The relative reactivity of o-acylanilines bearing various substituents was investigated by competition experiments, and it was found that electron-donating substituents increase the relative facileness of the C-N bond cleavage in both stoichiometric and catalytic reactions. The trend observed here is different from the one observed for the previously reported tantalum-mediated C-N bond cleavage.

AB - The reactivity of various o-acylaniline derivatives with ruthenium complexes was examined. The reaction of o-acylanilines with RuH 2(CO)(PPh3)3 (1) or an activated ruthenium species formulated as "Ru(CO)(PPh3)3" (4) gave amido hydrido complexes 3 and aryl amido complexes 6 formed via N-H and C-N bond cleavage, respectively. Addition of olefins, such as vinylsilanes, accelerates the C-N bond cleavage. The aryl amido complexes 6 can provide the C-N arylation product upon treatment with arylboronates. The relative reactivity of o-acylanilines bearing various substituents was investigated by competition experiments, and it was found that electron-donating substituents increase the relative facileness of the C-N bond cleavage in both stoichiometric and catalytic reactions. The trend observed here is different from the one observed for the previously reported tantalum-mediated C-N bond cleavage.

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