Homoleptic Zincate-Promoted Room-Temperature Halogen-Metal Exchange of Bromopyridines

被引：32

作者：

Chau, Nguyet Trang Thanh ^{[1
]}

Meyer, Maxime ^{[1
]}

Komagawa, Shinsuke ^{[2
]}

Chevallier, Floris ^{[3
]}

Fort, Yves ^{[1
]}

Uchiyama, Masanobu ^{[2
]}

Mongin, Florence ^{[3
]}

Gros, Philippe C. ^{[1
]}

机构：

[1] Nancy Univ, CNRS, SOR, SRSMC, F-54506 Vandoeuvre Les Nancy, France

[2] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

[3] Univ Rennes 1, CNRS, UMR 6510, F-35042 Rennes, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2010年 / 16卷 / 41期

关键词：

bromopyridines; cross-coupling; halogen-metal exchange; lithium; zinc; LITHIUM EXCHANGE; SELECTIVE MONOSUBSTITUTION; SUBSTITUTED PYRIDINES; BUTYLLITHIUM; IODINATION; LITHIATION; FACILE; ORTHOLITHIATION; TMSCH2LI-LIDMAE; HETEROCYCLES;

D O I：

10.1002/chem.201001664

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 nBu(4)ZnLi(2)center dot TMEDA reagent (1/3 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine). This reactivity contrasted with that of tBu(4)ZnLi(2)center dot TMEDA, which was inefficient below one equivalent. DFT calculations allowed us to rationalize the formation of N center dot center dot center dot Li stabilized poly-pyridyl 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.

引用

页码：12425 / 12433

页数：9

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