Preparation of Polyfunctional Arylzinc Organometallics in Toluene by Halogen/Zinc Exchange Reactions.
alkoxides
lithium
metal/halogen exchange
organozinc reagents
toluene
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
09 Sep 2019
09 Sep 2019
Historique:
received:
03
06
2019
pubmed:
28
6
2019
medline:
28
6
2019
entrez:
28
6
2019
Statut:
ppublish
Résumé
A wide range of polyfunctional diaryl- and diheteroarylzinc species were prepared in toluene within 10 min to 5 h through an I/Zn or Br/Zn exchange reaction using bimetallic reagents of the general formula R'
Identifiants
pubmed: 31243862
doi: 10.1002/anie.201906898
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
12898-12902Informations de copyright
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Co-complex [EtZn(OR)⋅ROH] (R=CH2CH2N(CH3)CH2CH2N(CH3)2) has been spectroscopically characterized by 1H and 13C NMR analysis; see the Supporting Information. The structure of the neutral complex EtZn(OR) has been previously established by X-ray crystallography; see: M. S. Hill, G. Kociok-Köhn, K. C. Molloy, D. C. Stanton, Main Group Met. Chem. 2015, 38, 61.
A solvent screen showed that the halogen/zinc exchange cannot only be performed in hydrocarbons such as toluene or hexane, but also in other industrially friendly ethereal solvents such as 2-methyl-THF or MTBE.
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See the Supporting Information for further details.
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Further examples can be found in the Supporting Information.
Because of the poor solubility of the aryl iodides, the reactions generating 7 g, j, k, and n-q were performed in THF.
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pTolyllithium was prepared by a direct lithium insertion into 4-chlorotoluene; see: C. G. Screttas, B. R. Steele, M. Micha-Screttas, G. A. Heropoulos, Org. Lett. 2012, 14, 5680-5683.
Prior to addition of the catalyst system and the aryl iodide, TMSCl (0.8 equiv; 0 °C, 10 min) was added to quench the excess alkoxide.
The arylzinc complex formed in this reaction has limited solubility in [D8]toluene but was fairly soluble in [D8]THF. Its 13C NMR spectrum shows a diagnostic resonance at δ=155.71 ppm for Zn−C(aryl) (vs. δ=86.4 ppm for C−I in 2-iodoanisole). DOSY NMR studies are consistent with the formation of a heteroleptic [Ar2Zn(OR)2Li2] species.
CCDC 1918845 (12) and 1918846 (13, see the Supporting Information), contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre.
Et3ZnLi was prepared in [D8]toluene by co-complexation of EtLi and Et2Zn. Its reaction with three equiv of 2-iodoanisole was monitored by 1H NMR spectroscopy, revealing the formation of an ArEt2ZnLi species; see the Supporting Information for details.