Expanding Mg-Zn hybrid chemistry : inorganic salt effects in addition reactions of organozinc reagents to trifluoroacetophenone and the implications for a synergistic lithium-magnesium-zinc activation

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Armstrong, David R. and Clegg, William and Garcia-Alvarez, Pablo and Kennedy, Alan R. and McCall, Matthew D. and Russo, Luca and Hevia, Eva (2011) Expanding Mg-Zn hybrid chemistry : inorganic salt effects in addition reactions of organozinc reagents to trifluoroacetophenone and the implications for a synergistic lithium-magnesium-zinc activation. Chemistry - A European Journal, 17 (30). pp. 8333-8341. ISSN 1521-3765 (https://doi.org/10.1002/chem.201100866)

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Abstract

Numerous organic transformations rely on organozinc compounds made through salt-metathesis (exchange) reactions from organolithium or Grignard reagents with a suitable zinc precursor. By combining X-ray crystallography, NMR spectroscopy and DFT calculations, this study sheds new light on the constitution of the organometallic species involved in this important synthetic tool. Investigations into the metathesis reactions of equimolar amounts of Grignard reagents (RMgX) and ZnCl2 in THF led to the isolation of novel magnesium-zinc hybrids, [{(thf)(2)(mu-Cl)(3)ZnR}(2)] (R = Et, tBu, nBu or o-OMe-C6H4), which exhibit an unprecedented structural motif in mixed magnesium-zinc chemistry. Furthermore, theoretical modelling of the reaction of EtMgCl with ZnCl2 reveals that formation of the mixed-metal compound is thermodynamically preferred to that of the expected homometallic products, RZnCl and MgCl2. This study also assesses the alkylating ability of hybrid 3 towards the sensitive ketone trifluoroacetophenone, revealing a dramatic increase in the chemoselectivity of the reaction when LiCl is introduced as an additive. This observation, combined with recent related breakthroughs in synthesis, points towards the existence of a trilateral Li/Mg/Zn synergistic effect.

ORCID iDs

Armstrong, David R., Clegg, William, Garcia-Alvarez, Pablo, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, McCall, Matthew D., Russo, Luca and Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506;
CORE (COnnecting REpositories)