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Volumn 17, Issue 16, 2011, Pages 4470-4479

Shedding new light on ZnCl2-mediated addition reactions of Grignard reagents to ketones: Structural authentication of key intermediates and diffusion-ordered NMR studies

Author keywords

addition reactions; Grignard reagents; mixed metal chemistry; NMR spectroscopy; zincates

Indexed keywords

ALKOXIDE LIGANDS; ALKYLATION REACTIONS; CATALYTIC AMOUNTS; CHARACTERISATION; CHEMO-SELECTIVITY; DOSY NMR; GRIGNARD REAGENT; INORGANIC SALTS; MAGNESIATE; MAGNESIUM CHEMISTRY; METATHESIS REACTIONS; MIXED-METAL CHEMISTRY; MOLAR EQUIVALENT; NMR SPECTROSCOPY; NMR STUDIES; REDUCTION PRODUCTS; STRUCTURAL MOTIFS; STRUCTURAL SUPPORT; SYNERGIC EFFECTS; TRIFLUOROACETOPHENONE; ZINCATES;

EID: 79953715957     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201002544     Document Type: Article
Times cited : (43)

References (97)
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    • 1H NMR analyses of the remaining filtrate showed that its formation was almost quantitative.
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    • See Supporting Information for full experimental details and copies of NMR spectra.
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    • 1H NMR spectrum is probably due to removal of some of the magnesium-bound THF molecules when crystals of 1 are dried under vacuum.
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    • 2).
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    • Equilibria of this type have been previously studied in the context of homoleptic alkyl alkali-metal zincates, see
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    • We chose 1,2,3,4-tetraphenylnaphthalene (TPhN), 1-phenylnaphthalene (PhN) and tetramethylsilane (TMS) as internal standards for this study.
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    • 2(TMEDA)] using the same internal standards as for 1. Thus, whereas a good fit is observed between its estimated V using DOSY NMR with its calculated V (error -9%), a much greater degree of inaccuracy is obtained between its estimated FW and its actual FW value (error -22%).
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    • 8]THF were obtained from their optimised geometries. DFT calculations were used to obtain the optimised geometries of the molecules and ions using the Gaussian G03 computational package. The B3LYP density functionals and the 6-311G* basis set were employed in this exercise. For each optimised species a frequency analysis was performed and no imaginary frequencies were obtained.
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    • - cannot be ruled out in the solution constitution of 1 at room temperature (see Supporting Information).
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    • For an unusual example of a 1,6-addition of a sodium-zincate to benzophenone see:, E. Hevia, G. W. Honeyman, A. R. Kennedy, R. E. Mulvey, J. Am. Chem. Soc. 2005, 127, 13106.
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    • -] fails to react with benzophenone; however, we believe in this case this lack of reactivity is due to the steric bulk of the tert-butyl groups rather than the tris(alkyl)zinc constitution of the anion in the mixed-metal species.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.