Selective transformation of vicinal-disubstituted epoxides into ketones by homogeneous rhodium catalysts

David Milstein, Ouri Buchman, Jochanan Blum

Research output: Contribution to journalArticle

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Abstract

Chlorotris(triphenylphosphine)rhodium has been shown to catalyze the selective rearrangement of many vicinaldisubstituted epoxides to ketones between 150 and 210°C. Kinetic measurements for various frans-1,2-diarylethylene oxides and RhCl(PAr3)3 catalysts were carried out. The reaction rate was shown to increase by introduction of electron-donating substituents into either the catalyst ligands or the substrate. The catalysis is inferred to proceed in the following order: (a) dissociation of RhCl(PAr3)3, (b) reversible nucleophilic cis addition of the epoxide to the activated catalyst to give a Rh(III) hydride, (c) intramolecular hydrogen transfer from the rhodium atom to the noncoordinated oxirane carbon, (d) reductive elimination to form the ketone and activated catalyst. The data are compatible with the expression rate = k1k2[S][C]0/(k-1 + k2 + k1[S]) where [S] and [C]0 are substrate and initial catalyst concentration, respectively. Step c is considered rate determining on the basis of kinetic isotope effect measurements. Complexes RhCl(PAr3)3 have been shown to catalyze also an unusual carbon-carbon bond cleavage in stilbene oxides having potent electron-attracting substituents to yield benzaldehydes and polymers. Epoxides in which one aromatic ring is more electron attracting than the other form aldehydes with the least electronegative groups.

Original languageEnglish
Pages (from-to)2299-2308
Number of pages10
JournalJournal of Organic Chemistry
Volume42
Issue number13
Publication statusPublished - 1977

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Rhodium
Epoxy Compounds
Ketones
Catalysts
Carbon
Electrons
Benzaldehydes
Ethylene Oxide
Kinetics
Substrates
Aldehydes
Hydrides
Isotopes
Oxides
Catalysis
Reaction rates
Hydrogen
Polymers
Ligands
Atoms

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Selective transformation of vicinal-disubstituted epoxides into ketones by homogeneous rhodium catalysts. / Milstein, David; Buchman, Ouri; Blum, Jochanan.

In: Journal of Organic Chemistry, Vol. 42, No. 13, 1977, p. 2299-2308.

Research output: Contribution to journalArticle

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