Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes

Masumi Itazaki; Yasushi Nishihara; Hisami Takimoto; Chikako Yoda; Kohtaro Osakada

doi:10.1016/j.molcata.2005.06.045

Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes

Masumi Itazaki, Yasushi Nishihara, Hisami Takimoto, Chikako Yoda, Kohtaro Osakada

Research output: Contribution to journal › Article

15 Citations (Scopus)

Abstract

2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh₃)₃ and RhH(PPh₃)₄. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh₃)₃. RhH(CO)(PPh₃)₃ promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η³-anti- CH₂C{C(CH₂)Ph}CHCH₃](PPh₃) ₂ (2) at 50 °C and Rh{κ¹,η²- CH₂CH(Ph)C(CH₂)CHCH₂}(CO)(PPh₃) ₂ (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.

Original language	English
Pages (from-to)	65-71
Number of pages	7
Journal	Journal of Molecular Catalysis A: Chemical
Volume	241
Issue number	1-2
DOIs	https://doi.org/10.1016/j.molcata.2005.06.045
Publication status	Published - Nov 1 2005
Externally published	Yes

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Keywords

CC bond activation
Diene
Hydrido complex
Methylenecyclopropane
Rhodium

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

Cite this

Itazaki, M., Nishihara, Y., Takimoto, H., Yoda, C., & Osakada, K. (2005). Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes. Journal of Molecular Catalysis A: Chemical, 241(1-2), 65-71. https://doi.org/10.1016/j.molcata.2005.06.045

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title = "Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes",

abstract = "2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.",

keywords = "CC bond activation, Diene, Hydrido complex, Methylenecyclopropane, Rhodium",

author = "Masumi Itazaki and Yasushi Nishihara and Hisami Takimoto and Chikako Yoda and Kohtaro Osakada",

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T1 - Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes

AU - Itazaki, Masumi

AU - Nishihara, Yasushi

AU - Takimoto, Hisami

AU - Yoda, Chikako

AU - Osakada, Kohtaro

PY - 2005/11/1

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N2 - 2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.

AB - 2-Phenyl-1-methylenecyclopropane is isomerized into 2-phenyl-1,3-butadiene and 1-phenyl-1,3-butadiene in the presence of catalytic amounts of RhH(CO)(PPh3)3 and RhH(PPh3)4. The Rh-containing product of the reactions has a 2-phenyl-1-methylallyl (or 1-phenyl-1-methylallyl) ligand, and is formed also from the reaction of 2-phenyl-1,3-butadiene with RhH(CO)(PPh3)3. RhH(CO)(PPh3)3 promotes ring-opening isomerization of 4-phenyl-1-methylenespiro[2,2]pentane to afford Rh[η3-anti- CH2C{C(CH2)Ph}CHCH3](PPh3) 2 (2) at 50 °C and Rh{κ1,η2- CH2CH(Ph)C(CH2)CHCH2}(CO)(PPh3) 2 (3) at -35°C. X-ray crystallography of 2 shows the π-allylic ligand having a methyl group at anti position. The mechanism for formation of 2 via intermediate 3 is discussed.

KW - CC bond activation

KW - Diene

KW - Hydrido complex

KW - Methylenecyclopropane

KW - Rhodium

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10.1016/j.molcata.2005.06.045