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Rearrangement of 3-Rhoda-1,2-dioxolanes to Rhodium Formylmethyl Hydroxy Complexes

✍ Scribed by Monique Krom; Ruud G. E. Coumans; Jan M. M. Smits; Anton W. Gal


Publisher
John Wiley and Sons
Year
2002
Tongue
English
Weight
283 KB
Volume
41
Category
Article
ISSN
0044-8249

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Proposed as intermediates in the catalytic oxidation of olefins to ketones, 3-rhoda-1,2-dioxolanes (ΞΊ C ,O -2-peroxyethyl rhodium complexes) have now been prepared by oxygenation of solid [(N -ligand)Rh (ethene)]PF with air. This process leads to stable isomeric 3-rhoda-1,2-dioxolanes A and B. Upon

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2-(4-Hydroxyalkyl)-1,3-dioxolanes (3a/3b, 5-7) undergo an via the benzylic carbenium ion B and the 1,3-dioxolan-2ylium cation C, is supported by the stereochemistry of the acid-catalyzed rearrangement to give 2-hydroxyethyl alkanoic esters 8-11. The postulated mechanism, proceeding reaction and the