☆ 4.8 Article

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

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2010)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 132, 期 44, 页码 15610-15623

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ja105855v

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Chemistry, Multidisciplinary

资金

National Institutes of Health [GM39764, GM 077167]
Pfizer
Merck
Sanofi-Aventis

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摘要

Lithium diisopropylamide (LDA) in tetrahydrofuran at -78 degrees 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 <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.

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