Boosting conjugate addition to nitroolefins using lithium tetraorganozincates : synthetic strategies and structural insights

Dell'Aera, Marzia and Perna, Filippo Maria and Vitale, Paola and Altomare, Angela and Palmieri, Alessandro and Maddock, Lewis C. H. and Bole, Leonie J. and Kennedy, Alan R. and Hevia, Eva and Capriati, Vito (2020) Boosting conjugate addition to nitroolefins using lithium tetraorganozincates : synthetic strategies and structural insights. Chemistry - A European Journal, 26 (40). pp. 8742-8748. ISSN 1521-3765 (https://doi.org/10.1002/chem.202001294)

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Abstract

We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R 4ZnLi 2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R 4ZnLi 2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N',N'-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N',N'-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et 4ZnLi 2 into equimolar amounts of solvent-separated Et 3ZnLi and EtLi.

ORCID iDs

Dell'Aera, Marzia, Perna, Filippo Maria, Vitale, Paola, Altomare, Angela, Palmieri, Alessandro, Maddock, Lewis C. H., Bole, Leonie J., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Hevia, Eva and Capriati, Vito;
  • Item type:Article
    ID code:73299
    Dates:
    Date
    Event
    17 July 2020
    Published
    17 March 2020
    Published Online
    15 March 2020
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:22 Jul 2020 15:04
    Last modified:17 Nov 2024 12:32
    URI:https://strathprints.strath.ac.uk/id/eprint/73299
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