Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 44, Pages 15610-15623Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja105855v
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Funding
- National Institutes of Health [GM39764, GM 077167]
- Pfizer
- Merck
- Sanofi-Aventis
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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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