Synlett 2012; 23(19): 2749-2752
DOI: 10.1055/s-0032-1316555
cluster
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Oxidative Arylalkylation of Unactivated Alkenes: Dual C–H Bond Cleavage of Anilines and Acetonitrile

Hao Zhang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. of China, Fax: +86(21)64166128   Email: gliu@mail.sioc.ac.cn
,
Pinhong Chen
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. of China, Fax: +86(21)64166128   Email: gliu@mail.sioc.ac.cn
,
Guosheng Liu*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. of China, Fax: +86(21)64166128   Email: gliu@mail.sioc.ac.cn
› Author Affiliations
Further Information

Publication History

Received: 26 April 2012

Accepted after revision: 26 May 2012

Publication Date:
16 July 2012 (online)


Abstract

A palladium-catalyzed oxidative arylalkylation of unactivated alkenes involving dual C–H bond cleavage of arene and acetonitrile was developed. This reaction was promoted by pyridine as a ligand, and the ratio of palladium to pyridine is vital for this transformation. A series of nitrile-containing indolines were efficiently provided in moderate to good yields.

Supporting Information

 
  • References and Notes


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  • 14 General Procedure for Pd-Catalyzed Oxidative Arylalkylarion of 1 In a sealed dry glass tube, alkene 1a (37.8 mg, 0.02 mmol), Pd(OAc)2 (4.6 mg, 0.02 mmol), AgF (126.8 mg, 1.0 mmol), PhI(OCOt-Bu)2 (203.1 mg, 0.5 mmol), and pyridine (1.3 μL, 0.016 mmol) were dissolved in dry MeCN (2.0 mL). The mixture was stirred at 100 °C for 24 h. Then the solvent was removed under vacuum, and the residue was purified by column chromatography on silica gel to give the product 2a. 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.4 Hz, 1 H), 7.28–7.24 (m, 1 H), 7.09 (d, J = 4.0 Hz, 2 H), 3.98 (d, J = 10.8 Hz, 1 H), 3.78 (d, J = 10.4 Hz, 1 H), 2.24 (s, 3 H), 2.19–2.14 (m, 2 H), 2.04–1.99 (m, 2 H), 1.44 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 168.6, 142.2, 135.8, 128.6, 124.0, 122.0, 119.4, 117.0, 60.4, 43.0, 36.9, 26.4, 24.2, 12.8. HRMS (EI): m/z calcd [M+]: 228.1263; found: 228.1266