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 | |
| Publication status | Published - 2013 Jan 28 |
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ASJC Scopus subject areas
- Organic Chemistry
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Substituent effects on stoichiometric and catalytic cleavage of carbon-nitrogen bonds in aniline derivatives by ruthenium-phosphine complexes. / Koreeda, Tetsuro; Kochi, Takuya; Kakiuchi, Fumitoshi.
In: Organometallics, Vol. 32, No. 2, 28.01.2013, p. 682-690.Research output: Contribution to journal › Article
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TY - JOUR
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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U2 - 10.1021/om3011855
DO - 10.1021/om3011855
M3 - Article
VL - 32
SP - 682
EP - 690
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 2
ER -