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 › peer-review

16 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

Keywords

CC bond activation
Diene
Hydrido complex
Methylenecyclopropane
Rhodium

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

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10.1016/j.molcata.2005.06.045

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@article{2f5e6f569b394481b192a1ddecba9ea3,

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",

note = "Funding Information: This work was partially supported by a Grant-in-aid for Scientific Research for Young Chemists No. 13740412 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.",

year = "2005",

month = nov,

day = "1",

doi = "10.1016/j.molcata.2005.06.045",

language = "English",

volume = "241",

pages = "65--71",

journal = "Journal of Molecular Catalysis A: Chemical",

issn = "1381-1169",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

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

N1 - Funding Information: This work was partially supported by a Grant-in-aid for Scientific Research for Young Chemists No. 13740412 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

PY - 2005/11/1

Y1 - 2005/11/1

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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M3 - Article

AN - SCOPUS:25844524691

SN - 1381-1169

VL - 241

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EP - 71

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

IS - 1-2

ER -

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

Abstract

Keywords

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