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

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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

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