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Dynamics of the Lithium Amide/Alkyllithium Interactions: Mixed Dimers and Beyond

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Organo-di-Metallic Compounds (or Reagents)

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 47))

Abstract

This review summarizes detailed investigations on the enantioselective nucleophilic addition of organolithiums onto prochiral electrophilic substrates, one of the simplest reaction meant to create a C–C bond, using dipolar bimetallic systems. Interestingly, these very popular and useful chemical transformations, even if taught at the undergraduate level, have remained underdeveloped when it comes to their enantioselective versions. The systems we present consist of a nucleophilic organolithium (NuLi) in strong dipolar interaction with a second lithiated entity bearing the source of asymmetry, i.e., a chiral lithium amide (CLA) derived from a 3-aminopyrrolidine (3APLi). Several 1:1 3APLi/NuLi noncovalent mixed aggregates are described and their relevance to the enantioselective process is discussed. Since the Curtin–Hammett principle forbids to correlate the complexes to the final ee's of the products, we have run complementary experiments of which results led us to propose the participation of an ephemeral, but more reactive, triptych aggregate.

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Notes

  1. 1.

    A result that was obtained after “cleansing” the methyllithium solution from traces (5–10%) of LiCl naturally present in commercial vials. See [113].

  2. 2.

    The 1:1:1:0.67 3APLi/Alk1/Alk2/ArCHO ratio can also be read as 1.5:1.5:1.5:1.

  3. 3.

    Availability of the starting materials at the time of the study

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Authors and Affiliations

  1. IRCOF: Laboratoire COBRA, Université de Rouen, CNRS, INSA de Rouen, UMR 6014 & FR 3038, 76821, Mont Saint Aignan Cedex, France

    Anne Harrison-Marchand, Nicolas Duguet, Gabriella Barozzino-Consiglio, Hassan Oulyadi & Jacques Maddaluno

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  1. Anne Harrison-Marchand
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  2. Nicolas Duguet
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  3. Gabriella Barozzino-Consiglio
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  4. Hassan Oulyadi
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  5. Jacques Maddaluno
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Correspondence to Anne Harrison-Marchand or Jacques Maddaluno .

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  1. College of Chemistry, Peking University, Beijing, China

    Zhenfeng Xi

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Harrison-Marchand, A., Duguet, N., Barozzino-Consiglio, G., Oulyadi, H., Maddaluno, J. (2014). Dynamics of the Lithium Amide/Alkyllithium Interactions: Mixed Dimers and Beyond. In: Xi, Z. (eds) Organo-di-Metallic Compounds (or Reagents). Topics in Organometallic Chemistry, vol 47. Springer, Cham. https://doi.org/10.1007/3418_2014_75

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