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Homoleptic zincate-promoted room-temperature halogen-metal exchange of bromopyridines

Abstract : Homoleptic lithium tri- and tetraalkyl zincates were reacted with a set of bromopyridines. Efficient and chemoselective bromine-metal exchanges were realized at room temperature with a substoichiometric amount of nBu4ZnLi2*TMEDA reagent (1/3 equiv; TMEDA=N,N,N',N'-tetramethylethylenediamine). This reactivity contrasted with that of tBu4ZnLi2*TMEDA, which was inefficient below one equivalent. DFT calculations allowed us to rationalize the formation of N***Li stabilized polypyridyl zincates in the reaction. The one-pot difunctionalization of dibromopyridines was also realized using the reagent stoichiometrically. The direct creation of C Zn bonds in bromopyridines enabled us to perform efficient Negishi-type cross-couplings.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01010436
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Submitted on : Thursday, June 19, 2014 - 5:26:15 PM
Last modification on : Thursday, December 12, 2019 - 1:50:52 PM

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Nguyet Trang Thanh Chau, Maxime Meyer, Shinsuke Komagawa, Floris Chevallier, Yves Fort, et al.. Homoleptic zincate-promoted room-temperature halogen-metal exchange of bromopyridines. Chemistry - A European Journal, Wiley-VCH Verlag, 2010, 16, pp.12425-12433. ⟨10.1002/chem.201001664⟩. ⟨hal-01010436⟩

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