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Unusual steric effects in sulfonyl transfer reactions

Hinchliffe, Paul S., Wood, J. Matthew, Davis, Andrew M., Austin, Rupert P., Beckett, Paul R. and Page, Michael I. (2001) Unusual steric effects in sulfonyl transfer reactions. Perkin Transactions 2. pp. 1503-1505. ISSN 1472-779X

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Abstract

The hydrolysis of N-acyl--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 -sultams, the N-acyl derivatives are at least 106 more reactive than N-acylsulfonamides. However, the -substituted 4-isopropylidene -sultam is relatively unreactive and undergoes alkaline hydrolysis with C–N fission leaving the strained 4-membered -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--sultam shows similar behaviour with preferential C–N fission whereas the (E)-4-ethylidene isomer and 4-isopropyl--sultam revert to hydrolytic ring opening with S–N fission

Item Type: Article
Subjects: Q Science > Q Science (General)
Q Science > QD Chemistry
Schools: School of Applied Sciences
School of Applied Sciences > Biomolecular Sciences Research Centre
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Depositing User: Sara Taylor
Date Deposited: 14 Feb 2008 14:30
Last Modified: 20 Oct 2008 10:24
URI: http://eprints.hud.ac.uk/id/eprint/526

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