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Issue 8, 2015
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Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates: kinetic and thermodynamic control

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Abstract

The addition of n-butyllithium to alkenylthiocarbamates in the presence of (−)-sparteine or the (+)-sparteine surrogate leads to asymmetric carbolithiation, and returns enantiomerically enriched thiocarbamate derivatives of secondary thiols. In THF, with the (+)-sparteine surrogate, in situ aryl migration leads to an enantiomerically enriched tertiary thiol derivative. Remarkably, the two pseudoenantiomeric chiral ligands do not always give enantiomeric products, probably as a result of a complex interplay of kinetic and thermodynamic control. In situ IR and NMR studies of a stable, hindered lithiated thiocarbamate demonstrated its chemical and configurational stability over a period of hours at 0 °C.

Graphical abstract: Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates: kinetic and thermodynamic control

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Article information


Submitted
03 Nov 2014
Accepted
16 Dec 2014
First published
16 Dec 2014

Org. Biomol. Chem., 2015,13, 2330-2340
Article type
Paper
Author version available

Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates: kinetic and thermodynamic control

D. Castagnolo, L. Degennaro, R. Luisi and J. Clayden, Org. Biomol. Chem., 2015, 13, 2330
DOI: 10.1039/C4OB02329C

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