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Synthesis 2009(22): 3757-3764  
DOI: 10.1055/s-0029-1217014
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium(II)-Catalyzed ortho Arylation of 2-Phenylpyridines with Potassium Aryltrifluoroborates by C-H Functionalization

Jean-Ho Chua, Shiang-Lin Tsaib, Ming-Jung Wu*a
a Department of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan 804, Taiwan
Fax: +886(7)5253909; e-Mail: mijuwu@faculty.nsysu.edu.tw;
b Faculty of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, Taiwan 807, Taiwan
Further Information

Publication History

Received 8 June 2009
Publication Date:
23 September 2009 (online)

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Abstract

An efficient one-pot synthesis of ortho-arylated 2-phenylpyridine and pyridine derivatives by use of potassium aryltri­fluoroborates is presented. The optimal reaction conditions are as follows: the 2-phenylpyridine or pyridine derivative is treated with 2.5 equivalents of a potassium aryltrifluoroborate in the presence of 10 mol% palladium(II) acetate, three equivalents of copper(II) acetate, and two equivalents of p-benzoquinone in 1,4-dioxane at 120 ˚C for 24 hours. p-Benzoquinone is an important co-oxidant in the transmetalation-reductive elimination step. The kinetic isotope effect (k H/k D) for the C-H bond activation was determined to be 1.09. It indicates that the C-H bond cleavage does not occur in the rate-determining step.

Key words

C-H functionalization - potassium trifluoroborate - palladium catalyst - arylations - pyridines

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18

Four different equivalents (1, 2, 2.5, and 3) of potassium trifluoro(phenyl)borate(2a) were examined under the reaction conditions, and the yield of product 3a was determined to be 52%, 68%, 74%, and 75%, respectively. According to these results, 2.5 equivalents of potassium aryltrifluoroborates were chosen to be the optimal amount.

19

CCDC 715155 contains the supplementary crystallographic data of compound 3c. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

23

The optimal reaction conditions reported in the literature were followed; see ref. 9g.