The mechanism of the rearrangement of β-acyloxyalkyl radicals
- 1 January 1973
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of the Chemical Society, Perkin Transactions 2
- No. 6,p. 861-872
- https://doi.org/10.1039/p29730000861
Abstract
Determination of the distribution of products from decarbonylation of 2-formyl-1,1-dimethylethyl heptanoate (6d) and other esters of 3-hydroxy-3-methylbutanal, and from the reaction of tributylstannane with 2-bromo-1,1-dimethylethyl benzoate (11b), 2-bromo-1-methyl-1-phenylethyl acetate (11c), and similar bromo-esters, has enabled the rates of rearrangement of some β-acyloxyalkyl radicals to be evaluated. The kinetic data together with the results of reactions using 18O labelled substrates indicate that 1,2-acyloxy-transfer proceeds via a concerted mechanism involving a five-membered cyclic transition state. The rate of rearrangement of the 2-acetoxy-2-phenylpropyl radical (12c) by 1,2-aryl migration has also been determined.Keywords
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