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Activation and regioselectivity of five-membered cyclic thionocarbamates to nucleophilic attack

Awheda, Ismail; Saygili, Nezire; Garner, A. Christopher; Wallis, John D.


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    <subfield code="a">The cyclic thionocarbamate of alaninol undergoes nucleophilic attack by sulfur nucleophiles at 5-C to give 1-thiopropyl-2-amine derivatives when derivatised on nitrogen with a Boc group. Iodide under microwave conditions causes a rearrangement to the isomeric thiazolidinone, while "hard" nucleophiles react at the thione group to yield a variety of product types by subsequent C-N or C-O cleavage. X-ray crystallography studies showed that the N-Boc group reduces delocalisation of electron density from nitrogen into the thione group, and thus promotes activation of the ring to nucleophilic attack.</subfield>
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