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- W2050443193 abstract "Lithium diisopropylamide (LDA)-mediated ortholithiations of 2-fluoropyridine and 2,6-difluoropyridine in tetrahydrofuran at -78 °C were studied using a combination of IR and NMR spectroscopic and computational methods. Rate studies show that a substrate-assisted deaggregation of LDA dimer occurs parallel to an unprecedented tetramer-based pathway. Standard and competitive isotope effects confirm post-rate-limiting proton transfer. Autocatalysis stems from ArLi-catalyzed deaggregation of LDA proceeding via 2:2 LDA-ArLi mixed tetramers. A hypersensitivity of the ortholithiation rates to traces of LiCl derives from LiCl-catalyzed LDA dimer-monomer exchange and a subsequent monomer-based ortholithiation. Fleeting 2:2 LDA-LiCl mixed tetramers are suggested to be key intermediates. The mechanisms of both the uncatalyzed and catalyzed deaggregations are discussed. A general mechanistic paradigm is delineated to explain a number of seemingly disparate LDA-mediated reactions, all of which occur in tetrahydrofuran at -78 °C." @default.
- W2050443193 created "2016-06-24" @default.
- W2050443193 creator A5031892610 @default.
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- W2050443193 creator A5048433983 @default.
- W2050443193 creator A5056923743 @default.
- W2050443193 creator A5074374544 @default.
- W2050443193 date "2013-02-08" @default.
- W2050443193 modified "2023-09-23" @default.
- W2050443193 title "Lithium Diisopropylamide-Mediated Ortholithiation of 2-Fluoropyridines: Rates, Mechanisms, and the Role of Autocatalysis" @default.
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