Literature DB >> 20397635

Mechanism of lithium diisopropylamide-mediated substitution of 2,6-difluoropyridine.

Mihai S Viciu1, Lekha Gupta, David B Collum.   

Abstract

Treatment of 2,6-difluoropyridine with lithium diisopropylamide in THF solution at -78 degrees C effects ortholithiation quantitatively. Warming the solution to 0 degrees C converts the aryllithium to 2-fluoro-6-(diisopropylamino)pyridine. Rate studies reveal evidence of a reversal of the ortholithiation and a subsequent 1,2-addition via two monomer-based pathways of stoichiometries [ArH*i-Pr(2)NLi(THF)](double dagger) and [ArH*i-Pr(2)NLi(THF)(3)](double dagger). Computational studies fill in the structural details and provide evidence of a direct substitution without the intermediacy of a Meisenheimer complex.

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Year:  2010        PMID： 20397635      PMCID： PMC2872121          DOI： 10.1021/ja910834b

Source DB:  PubMed          Journal:  J Am Chem Soc        ISSN： 0002-7863            Impact factor:   15.419


  18 in total

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5.  Lithium diisopropylamide-mediated ortholithiation and anionic fries rearrangement of aryl carbamates: role of aggregates and mixed aggregates.

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Journal:  J Am Chem Soc       Date:  2006-10-25       Impact factor: 15.419

Review 6.  Lithium diisopropylamide: solution kinetics and implications for organic synthesis.

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  7 in total

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3.  Lithium diisopropylamide-mediated ortholithiation of 2-fluoropyridines: rates, mechanisms, and the role of autocatalysis.

Authors:  Lekha Gupta; Alexander C Hoepker; Yun Ma; Mihai S Viciu; Marc F Faggin; David B Collum
Journal:  J Org Chem       Date:  2013-02-08       Impact factor: 4.354

4.  Sodium Diisopropylamide in N,N-Dimethylethylamine: Reactivity, Selectivity, and Synthetic Utility.

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5.  1,4-addition of lithium diisopropylamide to unsaturated esters: role of rate-limiting deaggregation, autocatalysis, lithium chloride catalysis, and other mixed aggregation effects.

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6.  Regioselective lithium diisopropylamide-mediated ortholithiation of 1-chloro-3-(trifluoromethyl)benzene: role of autocatalysis, lithium chloride catalysis, and reversibility.

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7.  Case for Lithium Tetramethylpiperidide-Mediated Ortholithiations: Reactivity and Mechanisms.

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  7 in total

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