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Synlett 2012(1): 150-154  
DOI: 10.1055/s-0031-1290099
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© Georg Thieme Verlag Stuttgart ˙ New York

Highly Effective Recyclable Palladium-Catalyzed Ligand-Free Heck Reactions under Aerobic Conditions

Peng Sun, Xiaoming Qu, Tingyi Li, Yan Zhu, Hailong Yang, Zeyong Xing, Jincheng Mao*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. of China
Fax: +86(512)65880403; e-Mail: jcmao@suda.edu.cn;
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Publication History

Received 3 September 2011
Publication Date:
09 December 2011 (online)

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Abstract

An effective protocol was developed for the Heck coupling reactions between various aryl halides and olefins. In the presence of 2 mol% of Pd(OAc)2, the desired products could be obtained in good yields under ligand-free and aerobic conditions. The catalytic system could be easily recycled for five times with high efficiency.

Key words

coupling reactions - Heck reaction - aryl halides - olefins - ligand-free

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9

General Procedure for the Ligand-Free Palladium-Catalyzed Heck-Type Coupling Reactions of Aryl Halide and Terminal Olefin
A mixture of aryl halide (0.5 mmol), olefin (3.0 mmol), Pd(OAc)2 (2 mol%), K2CO3 (2 equiv), and TBAF (2 g) in a sealed tube was stirred under air atmosphere at 70 ˚C for the desired time until complete consumption of starting material as monitored by TLC. After the mixture was poured into Et2O, then the mixture was washed with H2O, extracted with EtOAc, dried over anhyd Na2SO4, filtered and evaporated under vacuum, and the residue was purified by flash column chromatography (PE or PE-EtOAc) to afford the corresponding coupling products.
( E )-Methyl Cinnamate
¹H NMR (400 MHz, CDCl3): δ = 3.82 (s, 3 H), 6.45 (d, J = 16.0 Hz, 1 H), 7.39 (t, J = 3.2 Hz, 3 H), 7.52-7.55 (m, 2 H), 7.71 (d, J = 16.0 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 52.1, 118.0, 128.4, 129.2, 130.6, 134.6, 145.2, 167.8 ppm. HRMS (ESI+): m/z calcd for [C10H10O2]+: 162.0681; found: 162.0679.