Triphenylphosphine as a Ligand for the Pd-Catalyzed Amination of Un­activated Aryl Chlorides with Anilines Promoted by Salicylaldimine

Tao-Ping Liu; Qiang Cheng; Wen-Jing Song; Liang-Zhen Cai; Xiao-Chun Tao

doi:10.1055/s-0032-1317173

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(16): 2333-2336
DOI: 10.1055/s-0032-1317173

letter

Triphenylphosphine as a Ligand for the Pd-Catalyzed Amination of Unactivated Aryl Chlorides with Anilines Promoted by Salicylaldimine

Tao-Ping Liu

School of Chemical and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253519 eMail: xctao@ecust.edu.cn

,

Qiang Cheng

School of Chemical and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253519 eMail: xctao@ecust.edu.cn

,

Wen-Jing Song

School of Chemical and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253519 eMail: xctao@ecust.edu.cn

,

Liang-Zhen Cai*

School of Chemical and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253519 eMail: xctao@ecust.edu.cn

,

Xiao-Chun Tao*

School of Chemical and Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. of China Fax: +86(21)64253519 eMail: xctao@ecust.edu.cn

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Abstract

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Abstract

An efficient and selective amination of unactivated aryl chlorides with anilines catalyzed by mixed ligand Pd catalytic system of Ph₃P–salicylaldimine has been developed for the preparation of diarylamines. The benzyne mechanism was ruled out based on experimental results.

Key words

amination reaction - aryl chloride - salicylaldimine - di-arylamine - triphenylphosphine

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Referenzen

References and Notes

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13 General Procedure for the Amination of Aryl Chlorides with Anilines In a Schlenk tube with a magnetic bar, L6 (9.8 mg, 4 mol%), Pd(PPh₃)₂Cl₂ (14.5 mg, 2 mol%), t-BuONa (280 mg, 3 mmol), aryl choride (1.5 mmol), and aniline (1 mmol) in o-xylene (8 mL) were placed under nitrogen. The resulting mixture was stirred at reflux for 12 h. The solvent was evaporated in vacuo, and the residue was purified by flash column chromatography (PE–EtOAc) to give the products 3a–q
14 Diphenylamine (3a) Yield 95%; white solid; mp 49–50 °C. ¹H NMR (400 MHz, CDCl₃): δ = 5.43 (br, 1 H), 6.82 (t, J = 7.4 Hz, 2 H), 6.96–6.98 (m, 4 H), 7.20 (m, 4 H)
15 2,2′,4,6,6′-Pentamethyldiphenylamine (3q) Yield 88%; white solid; mp 82–84 °C. ¹H NMR (400 MHz, CDCl₃): δ = 2.00 (s, 12 H), 2.25 (s, 3 H), 4.71 (br, 1 H), 6.78–6.82 (m, 3 H), 6.95 (s, 1 H), 6.98 (s, 1 H)

For the amination reaction of aryl chlorides though the benzyne mechanism, see:

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Zusatzmaterial

Supporting Information

Triphenylphosphine as a Ligand for the Pd-Catalyzed Amination of Un­activated Aryl Chlorides with Anilines Promoted by Salicylaldimine

Triphenylphosphine as a Ligand for the Pd-Catalyzed Amination of Unactivated Aryl Chlorides with Anilines Promoted by Salicylaldimine