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Volumn 15, Issue 29, 2009, Pages 7192-7202

Preparation of polyfunctional arylmagnesium, arylzinc, and benzylic zinc reagents by using magnesium in the presence of LiCl

Author keywords

Grignard reaction; Heterocycles; Insertion; Regioselectivity; Zinc

Indexed keywords

BENZYLIC; CARBON-BROMINE BONDS; COMPETITIVE REDUCTION; CYANO GROUPS; ETHYL ESTERS; FUNCTIONALIZED; GRIGNARD REACTION; HETEROCYCLES; IN-SITU TRAPPING; INSERTION; LARGE SCALE EXPERIMENTS; MAGNESIUM REAGENTS; METALATION; ORGANIC HALIDES; REGIO-SELECTIVE; ZINC INSERTION; ZINC REAGENTS;

EID: 67650601656     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200900575     Document Type: Article
Times cited : (161)

References (105)
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    • On the basis of quantum chemical, calculations using B3LYP (ref, 32a-c, exchange and correlation functionals to explore the potential energy surfaces, it can be stated that the different regioselectivities do not derive from different thermodynamic stabilities of the products, namely the magnesium or zinc reagents coordinated by solvent molecules. The 6-31.G** basis set (ref, 32d-g, was used for all. C, H, O, and N atoms and Ahlrichs' def2-SVP split-valence basis set (ref, 32h, was used for Mg and Zn atoms, as implemented in the Gaussian 03 program ref, 32i, The calculations also show that the regioselectivities of the zinc insertion correlate with the thermodynamically more stable ortho-insertion products. In contrast, the thermodynamically more stable products of the magnesium insertion also correlate with the experimentally disfavored ortho-insertion Grignard reagents. Computational, mechanistic analysis of possible insertion pathways, especially thermodynamic
    • On the basis of quantum chemical, calculations using B3LYP (ref. [32a-c]) exchange and correlation functionals to explore the potential energy surfaces, it can be stated that the different regioselectivities do not derive from different thermodynamic stabilities of the products, namely the magnesium or zinc reagents coordinated by solvent molecules. The 6-31.G** basis set (ref. [32d-g]) was used for all. C, H, O, and N atoms and Ahlrichs' def2-SVP split-valence basis set (ref. [32h]) was used for Mg and Zn atoms, as implemented in the Gaussian 03 program (ref. [32i]). The calculations also show that the regioselectivities of the zinc insertion correlate with the thermodynamically more stable ortho-insertion products. In contrast, the thermodynamically more stable products of the magnesium insertion also correlate with the experimentally disfavored ortho-insertion Grignard reagents. Computational, mechanistic analysis of possible insertion pathways, especially thermodynamic analysis of radical stabilities and bond deformation energy analysis, could explain the experimental, results for zinc insertion, but could not rationalize the generation of the observed para-inserted magnesium reagents.
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