Cyanation of Unactivated Aryl Chlorides and Aryl Mesylates Catalyzed by Palladium and Hemilabile MOP-Type Ligands

Yahui Tu; Yi Zhang; Sheng Xu; Zhaoguo Zhang; Xiaomin Xie

doi:10.1055/s-0034-1379483

Synlett, Table of Contents

Synlett 2014; 25(20): 2938-2942
DOI: 10.1055/s-0034-1379483

letter

Cyanation of Unactivated Aryl Chlorides and Aryl Mesylates Catalyzed by Palladium and Hemilabile MOP-Type Ligands

Yahui Tu

^aSchool of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China

,

Yi Zhang

^bSchool of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. of China Fax: +86(21)54748925 Email: xiaominxie@sjtu.edu.cn

,

Sheng Xu*

^aSchool of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China

,

Zhaoguo Zhang

^bSchool of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. of China Fax: +86(21)54748925 Email: xiaominxie@sjtu.edu.cn

,

Xiaomin Xie*

^bSchool of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. of China Fax: +86(21)54748925 Email: xiaominxie@sjtu.edu.cn

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Abstract

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Abstract

Palladium-catalyzed cyanation of aryl halides and pseudo halides with potassium hexacyanoferrate is described employing the hemilabile, bulky, and electron-rich MOP-type ligands. When the mixture of t-BuOH and H₂O was used as the solvent and K₂CO₃ as the base, the MOP-type ligands showed high efficiency for the palladium-catalyzed cyanation. The effect of ligand structure was studied in detail, and 2-di-tert-butylphosphino-2′-isopropoxy-1,1′-binaphthyl was the more effective for the cyanation. The catalyst system allows the cyanation of unactivated aryl chlorides, and even aryl mesylates to occur in good yields. Furthermore, the reactivity of different arylated reagents in the catalytic system was found to be: ArBr > ArCl >> ArOMs > ArOSO₂Im > ArOSO₂NMe₂.

Key words

palladium - monophosphine ligands - cyanation - aryl chlorides - aryl mesylates

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References

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27 General Procedures for the Cyanation of Aryl Chlorides and Mesylates An oven-dried Schlenk tube was evacuated and backfilled with nitrogen. The Schlenk tube was charged with Pd(OAc)₂ (4.5 mg, 0.02 mmol ), L1 (36.5 mg, 0.08 mmol), PhB(OH)₂ (6.1 mg, 0.05 mmol), and t-BuOH (2 mL), and the mixture was stirred for half hour at 50 °C. After cooling to r.t., aryl chloride or mesylates (1.00 mmol), K₄[Fe(CN)₆]·3H₂O (211.2 mg, 0.50 mmol), K₂CO₃ (138.2 mg, 1.00 mmol), and H₂O (2 mL) were added. The septum was replaced with an inside reflux condenser, and then the Schlenk tube was placed in an oil bath preheated to 100 °C (120 °C for aryl mesylates) with stirring for 6 h (24 h for aryl mesylates). Then the reaction mixture was allowed to cool to r.t., extracted with CH₂Cl₂, and concentrated under reduced pressure. The crude material was purified by column chromatography on silica gel.4-(tert-Butyl)benzonitrile (2a) The crude material was purified by column chromatography on silica gel (eluting with PE–EtOAc, 20:1) to give the compound as yellow oil (127.4 mg, 80%). ¹H NMR (400 MHz, CDCl₃): δ = 7.61–7.57 (m, 2 H), 7.50–7.46 (m, 2 H), 1.33 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 156.4, 131.7, 126.0, 118.9, 109.1, 35.1, 30.8.

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