Unusual steric effects in sulfonyl transfer reactions

Paul S. Hinchliffe, J. Matthew Wood, Andrew M. Davis, Rupert P. Austin, R. Paul Beckett, Michael I. Page

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The hydrolysis of N-acyl-β-sultams generally occurs with ring opening and S-N fission in contrast to the C-N fission observed in analogous acyclic N-acyl sulfonamides. Similar to other β-sultams, the N-acyl derivatives are at least 106 more reactive than N-acylsulfonamides. However, the α-substituted 4-isopropylidene β-sultam is relatively unreactive and undergoes alkaline hydrolysis with C-N fission leaving the strained 4-membered β-sultam ring intact. This reduction in reactivity is shown to be due to steric strain introduced in the transition state for attack at the sulfonyl centre. (Z)-4-Ethylidene-β-sultam shows similar behaviour with preferential C-N fission whereas the (E)-4-ethylidene isomer and 4-isopropyl-β-sultam revert to hydrolytic ring opening with S-N fission.

LanguageEnglish
Pages1503-1505
Number of pages3
JournalJournal of the Chemical Society, Perkin Transactions 2
Volume9
DOIs
Publication statusPublished - 2001

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Hydrolysis
Sulfonamides
Isomers
beta-sultam
Derivatives
propylene

Cite this

Hinchliffe, P. S., Wood, J. M., Davis, A. M., Austin, R. P., Beckett, R. P., & Page, M. I. (2001). Unusual steric effects in sulfonyl transfer reactions. Journal of the Chemical Society, Perkin Transactions 2, 9, 1503-1505. https://doi.org/10.1039/b104923m
Hinchliffe, Paul S. ; Wood, J. Matthew ; Davis, Andrew M. ; Austin, Rupert P. ; Beckett, R. Paul ; Page, Michael I. / Unusual steric effects in sulfonyl transfer reactions. In: Journal of the Chemical Society, Perkin Transactions 2. 2001 ; Vol. 9. pp. 1503-1505.
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Hinchliffe, PS, Wood, JM, Davis, AM, Austin, RP, Beckett, RP & Page, MI 2001, 'Unusual steric effects in sulfonyl transfer reactions', Journal of the Chemical Society, Perkin Transactions 2, vol. 9, pp. 1503-1505. https://doi.org/10.1039/b104923m

Unusual steric effects in sulfonyl transfer reactions. / Hinchliffe, Paul S.; Wood, J. Matthew; Davis, Andrew M.; Austin, Rupert P.; Beckett, R. Paul; Page, Michael I.

In: Journal of the Chemical Society, Perkin Transactions 2, Vol. 9, 2001, p. 1503-1505.

Research output: Contribution to journalArticle

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AU - Hinchliffe, Paul S.

AU - Wood, J. Matthew

AU - Davis, Andrew M.

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AB - The hydrolysis of N-acyl-β-sultams generally occurs with ring opening and S-N fission in contrast to the C-N fission observed in analogous acyclic N-acyl sulfonamides. Similar to other β-sultams, the N-acyl derivatives are at least 106 more reactive than N-acylsulfonamides. However, the α-substituted 4-isopropylidene β-sultam is relatively unreactive and undergoes alkaline hydrolysis with C-N fission leaving the strained 4-membered β-sultam ring intact. This reduction in reactivity is shown to be due to steric strain introduced in the transition state for attack at the sulfonyl centre. (Z)-4-Ethylidene-β-sultam shows similar behaviour with preferential C-N fission whereas the (E)-4-ethylidene isomer and 4-isopropyl-β-sultam revert to hydrolytic ring opening with S-N fission.

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