The mechanism of the β-acyloxyalkyl radical rearrangement: Kinetic and 18O-labelling studies

Athelstan L.J. Beckwith; Peter J. Duggan

doi:10.1039/p29920001777

The mechanism of the β-acyloxyalkyl radical rearrangement: Kinetic and ¹⁸O-labelling studies

Athelstan L.J. Beckwith
, Peter J. Duggan

Research output: Contribution to journal › Article › peer-review

35 Citations (Scopus)

Abstract

Experiments with ¹⁸O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.

Original language	English
Pages (from-to)	1777-1783
Number of pages	7
Journal	Journal of the Chemical Society, Perkin Transactions 2
Issue number	10
DOIs	https://doi.org/10.1039/p29920001777
Publication status	Published - 1992
Externally published	Yes

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abstract = "Experiments with 18O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24\% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.",

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N2 - Experiments with 18O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.

AB - Experiments with 18O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.

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JF - Journal of the Chemical Society, Perkin Transactions 2

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ER -

The mechanism of the β-acyloxyalkyl radical rearrangement: Kinetic and ¹⁸O-labelling studies

Abstract

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