Tetramethylguanidine as an Inexpensive and Efficient Ligand for the Palladium-Catalyzed Heck Reaction

Shenghai Li; Haibo Xie; Suobo Zhang; Yingjie Lin; Jianing Xu; Jungang Cao

doi:10.1055/s-2005-871581

LETTER

Tetramethylguanidine as an Inexpensive and Efficient Ligand for the Palladium-Catalyzed Heck Reaction

Shenghai Li^b, Haibo Xie^a, Suobo Zhang*^a, Yingjie Lin^b, Jianing Xu^b, Jungang Cao^b
^a State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Graduate School of Chinese Academy of Sciences, Changchun 130022, P. R. China
^b College of Chemistry, Jilin University, Changchun 130023, P. R. China
e-Mail: sbzhang@ciac.jl.cn;

Abstract

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Abstract

An inexpensive and efficient Pd(OAc)₂/tetramethylguanidine (TMG) or PdCl₂/TMG catalytic system has been developed for the Heck reaction of an olefin with an aryl halide. The TONs were up to 1000000 when iodobenzene was used as the substrate with butyl acrylate as the reactant. In addition, [Pd(TMG)₄]Cl₂(H₂O)₈, an air-stable compound, effectively promoted the Heck reaction, which demonstrated that TMG acted as a ligand in this reaction system.

Key words

tetramethylguanidine - Heck reaction - palladium - aryl halides - ligand

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References

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Single crystals of complex [Pd(TMG)₄]Cl₂(H₂O)₈ suitable for X-ray diffraction were obtained by slow diffusion of hexane into a dichloromethane solution of PdCl₂/TMG. The compound crystallizes in the triclinic space group P-1 with a = 8.9997 (11) Å, b = 10.3817 (13) Å, c = 11.6080 (14) Å, α = 78.040 (2)°, β = 68.603 (2)°, γ = 82.922 (2)°, V = 986.5 (2) Å³, R1 = 0.0309, wR = 0.0894.

Typical Procedure for the Heck Reaction: An oven-dried Schlenk flask was charged under N₂ with styrene (6.0 mmol), bromobenzene (5.0 mmol), and NaOAc (6.0 mmol). A solution of catalyst Pd(OAc)₂/TMG (1:4) or PdCl₂/TMG (1:4) in DMA (5.0 mL, 1.0 × 10^-6 M) was then added via syringe. The flask was sealed and placed in a 140 °C oil bath and stirred for 20 h. The course of the reaction was monitored by periodically taking samples and analyzing them by gas chromatography [di(ethylene glycol)-Bu₂O as internal standard]. After cooling to r.t., the reaction mixture was poured into H₂O (50 mL) and extracted with EtOAc (3 × 40 mL). The combined organic extracts were washed with brine, dried (Na₂SO₄), and concentrated. Purification by flash chromatography on silica gel (hexanes-CH₂Cl₂,
1:1) gave trans-stilbene (859 mg, 95.5%), estimated to be >99% pure by ¹H NMR and GC.