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

Castagnolo, Daniele, Degennaro, Leonardo, Luisi, Renzo and Clayden, Jonathan (2015) Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates: kinetic and thermodynamic control. Organic and Biomolecular Chemistry, 13 (8). pp. 2330-2340. ISSN 1477-0520

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Official URL: http://dx.doi.org/10.1039/c4ob02329c

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.

Item Type: Article
Subjects: F100 Chemistry
Department: Faculties > Health and Life Sciences > School of Life Sciences > Applied Sciences
Depositing User: Becky Skoyles
Date Deposited: 27 Feb 2015 16:10
Last Modified: 28 Sep 2015 13:26
URI: http://nrl.northumbria.ac.uk/id/eprint/21507

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