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

Tetsuro Koreeda; Takuya Kochi; Fumitoshi Kakiuchi

doi:10.1021/om3011855

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

Tetsuro Koreeda, Takuya Kochi, Fumitoshi Kakiuchi

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

35 Citations (Scopus)

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 language	English
Pages (from-to)	682-690
Number of pages	9
Journal	Organometallics
Volume	32
Issue number	2
DOIs	https://doi.org/10.1021/om3011855
Publication status	Published - 2013 Jan 28

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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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.",

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

Abstract

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