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

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

Research output: Contribution to journalArticle

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{κ12- 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 languageEnglish
Pages (from-to)65-71
Number of pages7
JournalJournal of Molecular Catalysis A: Chemical
Volume241
Issue number1-2
DOIs
Publication statusPublished - Nov 1 2005
Externally publishedYes

Fingerprint

Carbon Monoxide
butadiene
Isomerization
Butadiene
isomerization
rings
Ligands
ligands
X ray crystallography
pentanes
crystallography
products
methylenecyclopropane
x rays
1,3-butadiene

Keywords

  • CC bond activation
  • Diene
  • Hydrido complex
  • Methylenecyclopropane
  • Rhodium

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology
  • Materials Science (miscellaneous)

Cite this

Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes. / Itazaki, Masumi; Nishihara, Yasushi; Takimoto, Hisami; Yoda, Chikako; Osakada, Kohtaro.

In: Journal of Molecular Catalysis A: Chemical, Vol. 241, No. 1-2, 01.11.2005, p. 65-71.

Research output: Contribution to journalArticle

Itazaki, Masumi ; Nishihara, Yasushi ; Takimoto, Hisami ; Yoda, Chikako ; Osakada, Kohtaro. / Ring-opening isomerization of methylenecyclopropanes catalyzed by hydridorhodium(I) complexes. In: Journal of Molecular Catalysis A: Chemical. 2005 ; Vol. 241, No. 1-2. pp. 65-71.
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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

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