Heck Reaction of Vinyl Bromides with Alkenes in the Presence of a Tetra­phosphine/Palladium Catalyst

Abstract

Through the use of [PdCl(C₃H₅)]₂-cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as a catalyst, a range of vinyl bromides undergo Heck reaction with a wide variety of alkenes leading selectively to the corresponding 1,3-dienes in good yields. Furthermore, it can be used at low loading even for reactions of sterically hindered vinyl bromides.

catalysis - palladium - tetraphosphine - alkenes - vinyl bromides

References

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1b Heck RF. Vinyl Substitution with Organopalladium Intermediates, in Comprehensive Organic Synthesis   Vol. 4:  Trost BM. Fleming I. Pergamon; Oxford: 1991. 

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5 For a review on the synthesis of polypodal diphenyl-phosphine ligands, see: Laurenti D. Santelli M. Org. Prep. Proc. Int.  1999,  31:  245 

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9

As a typical experiment, the reaction of β-bromostyrene (1.83 g, 10 mmol), n-butyl acrylate (2.56 g, 20 mmol) and K₂CO₃ (2.8 g, 20 mmol) at 130 °C during 20 h in anhydrous DMF (10 mL) in the presence of cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl) cyclopentane/[PdCl(C₃H₅)]₂ complex (0.0001 mmol) under argon affords the corresponding adduct after extraction with dichloro-methane, evaporation and filtration on silica gel (pentane/diethyl ether: 1/1) in 66% (1.52 g) isolated yield. n-Butyl (E,E)-5-phenylpenta-2,4-dienoate, ¹H NMR (300 MHz, CDCl₃): δ = 7.45 (d, J = 7.4 Hz, 2 H, Ph), 7.45-7.25 (m, 4 H, Ph and =CH), 6.89 (m, 2 H, =CH), 5.98 (d, J = 15.3 Hz, 1 H, =CH), 4.15 (t, J = 6.6 Hz, 2 H, CH₂), 1.65 (m, 2 H, CH₂), 1.40 (m, 2 H, CH₂), 0.94 (t, J = 7.4 Hz, 1 H, Me).

10

¹H NMR (300 MHz, CDCl₃) of selected products: Entry 17: δ = 7.50-7.15 (m, 5 H, Ph), 6.75 (dd, J = 10.9, 15.7 Hz, 1 H, =CH), 6.43 (d, J = 15.7 Hz, 1 H, =CH), 6.19 (dd, J = 10.9, 15.1 Hz, 1 H, =CH), 5.82 (dt, J = 15.1, 7.0 Hz, 1 H, =CH), 1.50-1.15 (m, 12 H, 6 CH₂), 1.15 (m, 2 H, CH₂), 0.88 (t, J = 6.8 Hz, 3 H, CH₃); Entry 24: δ = 7.40 (d, J = 7.7 Hz, 2 H, Ph), 7.29 (t, J = 7.2 Hz, 2 H, Ph), 7.17 (t, J = 7.2 Hz, 1 H, Ph), 6.74 (d, J = 16.2 Hz, 1 H, =CH), 6.47 (d, J = 16.2 Hz, 1 H, =CH), 5.86 (t, J = 8.3 Hz, 1 H, =CH), 2.51 (m, 2 H, CH₂), 2.25 (m, 2 H, CH₂), 1.70-1.40 (m, 8 H, 4 CH₂); Entry 26:
δ = 7.32 (d, J = 15.9 Hz, 1 H, =CH) 5.93 (d, J = 15.9 Hz, 1 H, =CH), 5.36 (s, 1 H, =CH₂), 5.33 (s, 1 H, =CH₂), 4.15 (t,
J = 6.8 Hz, 2 H, CH₂), 2.24 (q, J = 7.3 Hz, 2 H, CH₂), 1.42 (m, 2 H, CH₂), 1.65 (m, 2 H, CH₂), 1.11 (t, J = 7.3 Hz, 3 H, CH₃), 0.94 (t, J = 7.3 Hz, 3 H, CH₃); Entry 29: δ = 7.34 (d, J = 8.7 Hz, 2 H, Ar), 6.86 (d, J = 8.7 Hz, 2 H, Ar), 6.70 (d, J = 16.2 Hz, 1 H, =CH), 6.53 (d, J = 16.2 Hz, 1 H, =CH), 5.07 (s, 1 H, =CH₂), 5.01 (s, 1 H, =CH₂), 3.80 (s, 3 H, OMe), 2.34 (q, J = 7.3 Hz, 2 H, CH₂), 1.15 (t, J = 7.3 Hz, 3 H, CH₃); Entry 30: δ = 7.58 (d, J = 8.5 Hz, 2 H, Ar), 7.48 (d, J = 8.5 Hz, 2 H, Ar), 6.90 (d, J = 16.4 Hz, 1 H, =CH), 6.55 (d, J = 16.4 Hz, 1 H, =CH), 5.22 (s, 1 H, =CH₂), 5.19 (s, 1 H, =CH₂), 2.36 (q, J = 7.3 Hz, 2 H, CH₂), 1.16 (t, J = 7.3 Hz, 3 H, CH₃); Entry 32: δ = 8.52 (m, 2 H, Ar), 7.26 (m, 2 H, Ar), 6.99 (d,
J = 16.4 Hz, 1 H, =CH), 6.47 (d, J = 16.4 Hz, 1 H, =CH), 5.23 (s, 1 H, =CH₂), 5.20 (s, 1 H, =CH₂), 2.34 (q, J = 7.3 Hz, 2 H, CH₂), 1.16 (t, J = 7.3 Hz, 3 H, CH₃); Entry 33: δ = 7.54 (dd, J = 11.7, 15.2 Hz, 1 H, =CH), 5.97 (d, J = 11.7 Hz, 1 H, =CH), 5.75 (d, J = 15.2 Hz, 1 H, =CH), 4.15 (t, J = 6.8 Hz, 2 H, CH₂), 1.88 (s, 3 H, CH₃), 1.86 (s, 3 H, CH₃), 1.65 (m, 2 H, CH₂), 1.40 (m, 2 H, CH₂), 0.94 (t, J = 7.3 Hz, 3 H, CH₃); Entry 37: δ = 8.51 (m, 2 H, Ar), 7.15 (m, 2 H, Ar), 7.17 (dd, J = 11.0 Hz, 15.5 Hz, 1 H, =CH), 6.32 (d, J = 15.5 Hz, 1 H, =CH), 6.02 (d, J = 11.0 Hz, 1 H, =CH), 1.88 (s, 3 H, CH₃), 1.87 (s, 3 H, CH₃); Entry 38: δ = 7.86 (d, J = 15.5 Hz, 1 H, =CH), 5.77 (d, J = 15.5 Hz, 1 H, =CH), 4.15 (q, J = 6.8 Hz, 2 H, CH₂), 1.95 (s, 3 H, CH₃), 1.86 (s, 3 H, CH₃), 1.78 (s, 3 H, CH₃), 1.65 (m, 2 H, CH₂), 1.40 (m, 2 H, CH₂), 0.94 (t,
J = 7.3 Hz, 3 H, CH₃); Entry 41: δ = 8.51 (m, 2 H, Ar), 7.48 (d, J = 15.9 Hz, 1 H, =CH), 7.25 (m, 2 H, Ar), 6.35 (d, J = 15.9 Hz, 1 H, = CH), 1.96 (s, 3 H, CH₃), 1.88 (s, 6 H, 2 CH₃); Entry 42: δ = 7.41 (d, J = 7.4 Hz, 2 H, Ph); 7.31 (t, J = 7.4 Hz, 2 H, Ph), 7.23 (t, J = 7.4 Hz, 1 H, Ph), 6.81 (d, J = 16.2 Hz, 1 H, =CH), 6.60 (d, J = 16.2 Hz, 1 H, =CH), 5.26 (s, 1 H, =CH₂), 5.14 (s, 1 H, =CH₂), 3.82 (t, J = 6.5 Hz, 2 H, CH₂), 2.64 (t, J = 6.5 Hz, 2 H, CH₂).