Cis-trans isomerization of epoxides catalyzed by ruthenium(II) porphyrins

Journal Article · Wed Jun 22 00:00:00 EDT 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00221a021· OSTI ID:5993308

Groves, J T; Ahn, K H; Quinn, R

Bis(tetrahydrofuran)(5,10,15,20-tetramesitylporphyrinato)ruthenium(II) (Ru/sup II/TMP(THF)/sub 2/) and the corresponding p-tolylporphyrin (Ru/sup II/TTP(THF)/sub 2/) have been found to catalyze the cis-trans isomerization of epoxides under mild conditions. For ..beta..-methylstyrene oxide an equilibrium ratio of 5.4:1 (trans/cis) was achieved with either isomer indicating a free energy difference of 1 kcal/mol. Inhibition of the isomerization by added olefins was observed and attributed to olefin coordination to ruthenium(II). cis-..beta..-Methylstyrene oxide readily formed and adduct with Ru/sup II/TMP(CO), while the trans isomer did not. The isomerization of trans-(1S,2S)-..beta..-methylstyrene oxide gave only cis-(1R,2S)-..beta..-methylstyrene oxide gave only the cis-(1R,2S)-..beta..-methylstyrene oxide. A mechanism for epoxide isomerization involving homolytic cleavage of the C/sub 1/-O bond to give carbon radical intermediate is proposed.

• Research Organization: Princeton Univ., NJ (USA)
• OSTI ID: 5993308
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:13; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CARBOXYLIC ACIDS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
EPOXIDES
EQUILIBRIUM
EXPERIMENTAL DATA
FREE ENTHALPY
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
ISOMERIZATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
PORPHYRINS
RUTHENIUM COMPLEXES
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES