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Lithium hexamethyldisilazide-mediated enolizations: influence of triethylamine on E/Z selectivities and enolate reactivities.

ABSTRACT: Lithium hexamethyldisilazide (LiHMDS) in triethylamine (Et 3N)/toluene is shown to enolize acyclic ketones and esters rapidly and with high E/ Z selectivity. Mechanistic studies reveal a dimer-based mechanism consistent with previous studies of LiHMDS/Et 3N. E/ Z equilibration occurs when <2.0 equiv of LiHMDS are used. Studies of the aldol condensation and Ireland-Claisen rearrangement of the resulting Et 3N-solvated enolates show higher and often complementary diastereoselectivities when compared with analogous reactions in THF. The Et 3N-solvated enolates also display a marked (20-fold) acceleration of the Ireland-Claisen rearrangement with evidence of autocatalysis. A possible importance of amine-solvated enolates is discussed.

SUBMITTER: Godenschwager PF

PROVIDER: S-EPMC3021125 | BioStudies | 2008-01-01

REPOSITORIES: biostudies

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