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

Daniele Castagnolo, Leonardo Degennaro, Renzo Luisi, Jonathan Clayden

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)2330-2340
JournalOrganic and Biomolecular Chemistry
Volume13
Issue number8
DOIs
Publication statusPublished - 2015

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