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. 2014 Jun 18;136(24):8568-76.
doi: 10.1021/ja504886x. Epub 2014 Jun 3.

General method for functionalized polyaryl synthesis via aryne intermediates

Thanh Truong  1 , Milad Mesgar, Ky Khac Anh Le, Olafs Daugulis
Affiliations

General method for functionalized polyaryl synthesis via aryne intermediates

Thanh Truong et al. J Am Chem Soc. .

Abstract

A method for base-promoted arylation of arenes and heterocycles by aryl halides and aryl triflates is described. Additionally, in situ electrophilic trapping of ArLi intermediates generated in the reaction of benzyne with deprotonated arenes or heterocycles has been developed, providing rapid and easy access to a wide range of highly functionalized polyaryls. Base-promoted arylation methodology complements transition-metal-catalyzed direct arylation and allows access to structures that are not easily accessible via other direct arylation methods. The reactions are highly functional-group tolerant, with alkene, ether, dimethylamino, trifluoromethyl, ester, cyano, halide, hydroxyl, and silyl functionalities compatible with reaction conditions.

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Figures

Scheme 1
Scheme 1. Mechanism of Base-Promoted Arylation of Heterocycle and Arene C–H Bonds
Scheme 2
Scheme 2. Buchwald’s SPhos Ligand Synthesis
Scheme 3
Scheme 3. Reactions of Heterocyclic Arynes
See this image and copyright information in PMC

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