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Lithium diisopropylamide (LDA) in tetrahydrofuran at -78 °C undergoes 1,4-addition to an unsaturated ester via a rate-limiting deaggregation of LDA dimer followed by a post-rate-limiting reaction with the substrate. Muted autocatalysis is traced to a lithium enolate-mediated deaggregation of the LDA dimer and the intervention of LDA-lithium enolate mixed aggregates displaying higher reactivities than LDA. Striking accelerations are elicited by &lt;1.0 mol % LiCl. Rate and mechanistic studies have revealed that the uncatalyzed and catalyzed pathways funnel through a common monosolvated-monomer-based intermediate. Four distinct classes of mixed aggregation effects are discussed.

journal of the american chemical society

1,4-Addition of Lithium Diisopropylamide to Unsaturated Esters: Role of Rate-Limiting Deaggregation, Autocatalysis, Lithium Chloride Catalysis, and Other Mixed Aggregation Effects