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.

Original languageEnglish
Pages (from-to)1503-1505
Number of pages3
JournalJournal of the Chemical Society, Perkin Transactions 2
Volume9
DOIs
Publication statusPublished - 2001

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    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