Final Thoughts on Chemistry for 20439-47-8

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Stereoselective Protonation of Carbanions, 4. Enantioselective Protonation of Lactone Enolates

The prochiral lithium enolates derived from the five-membered lactones rac-1 and rac-2 were protonated by 37 OH- and 21 NH-chiral proton sources in THF at -78 deg C.The enantioselectivities, determined directly from the reaction mixture by chiral HPLC, are always higher for system 1, probably due to restricted rotation of the phenyl group in 1Li at low temperature (NMR) and range from 0-54percent ee.The strongest stereodifferentiation is observed if the OH or NH acids carry an adjacent O- or N-containing group (structures G-J0 which allows complexation with the lithium ion.A plausible transition state involving the dimeric lithium enolate is proposed. – Key Words: Protonation / Enantioselectivity / Lactone enolates / Chiral proton sources

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI