Enantioselective alkylation of lactams and lactones via lithium enolate formation using a chiral tetradentate lithium amide in the presence of lithium bromide
โ Scribed by Jun-ichi Matsuo; Shu Kobayashi; Kenji Koga
- Publisher
- Elsevier Science
- Year
- 1998
- Tongue
- French
- Weight
- 210 KB
- Volume
- 39
- Category
- Article
- ISSN
- 0040-4039
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โฆ Synopsis
Enantioselective alkylation of lactams and lactones can be realized up to 98% ee by deprotonation with a chiral tetradentate lithium amide (4b) in the presence of lithium bromide, and subsequent alkylation with active alkylating agents in non-chelating solvents.
๐ SIMILAR VOLUMES
An efficient enantioselective alkylation of the lithium enolates of cyclohexanone and ltetralone with reactive alkyl halides was realized using a stoichiometric amount of a tetradentate chiral amine as a ligand for the lithium in the presence of lithium bromide in toluene.
Ihe prochiral lithium 2,2,6-trimethylcyclohexenolate (2) was prepared from ketone 1 by deprotonation with lithium (S,S)-a,a'-dimethyldibenzylamide(4). Reaction of 2 with carbon dioxide at low temperature followed by methylation with metFy1 iodide yielded the corresponding ester 3 with an e.e. of 67%
Lithium N-trityl-N-(R)-1-phenylethylamide (6) is a readily available and useful reagent for the enantioselective (20:1) conversion of 4-t-butylcyclohexanone to the corresponding (S)-enolate. This reaction provides access to numerous useful chiral compounds.