Synthesis of Arylethylene or Diarylethylene Compounds by Pd-Catalyzed Heck Coupling Reaction

Abstract

We have developed an effective palladium-catalyzed arylation or diarylation couplings of olefins with various aryl halides in the presence of readily available ligands. This method is simple, economical, and practical for the synthesis of arylethylene and diarylethylene.

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GRAPHICAL ABSTRACT

Keywords:

• Arylation
• aryl halides
• coupling reactions
• Heck reaction
• olefins

ACKNOWLEDGMENTS

We are grateful to the grants from International S&T Cooperation Program of Jiangsu Province (BZ2010048), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry, the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Key Laboratory of Organic Synthesis of Jiangsu Province.

Notes

^a Catalytic conditions: iodobenzene (1.0 mmol), butyl acrylate (0.3 mmol), base (0.6 mmol), solvent (2 ml), 120 °C, 24 h, Ar.

^b Determined by GC-MS.

^c Isolated yield of diarylethylene.

^d DMSO.

^e PEG-400.

^f NMP.

^g DMAc.

^h At 130 °C.

ⁱ Iodobenzene (1.5 mmol).

^j Iodobenzene (1.8 mmol).

^a Reaction conditions: Aryl iodide (1.0 mmol), olefin (0.3 mmol), Pd(OAc)₂ (4 mol%), A (8 mol%), Cs₂CO₃ (0.6 mmol), DMF (2 ml), 120 °C, 24 h, Ar.

^b Isolated yield of diarylethylene.

^c GC yield using n-decane as internal standard, because arylethylene product and diarylethylene product cannot be separated by flash chromatography.

^d 48 h.

^a Reaction conditions: Iodobenzene (0.3 mmol), butyl acrylate (0.3 mmol), Pd(OAc)₂ (4 mol%), ligand (8 mol%), Cs₂CO₃ (0.6 mmol), DMF (2 ml), Ar.

^b Isolated yield of monoarylethylene.

^a Reaction conditions: Aryl iodide (0.3 mmol), olefin (0.3 mmol), Pd(OAc)₂ (4 mol%), F (8 mol%), Cs₂CO₃ (0.6 mmol), DMF (2 ml), Ar.

^b Isolated yield of monoarylethylene.