A Transition-Metal-Free Cross-Coupling Reaction of Allylic Bromides with Aryl- and Vinylboronic Acids

Abstract

A cross-coupling reaction between aryl- and vinylboronic acids and various allylic bromides proceeded without the use of a transition-metal catalyst to give the corresponding allylated products in moderate to good yields. The use of an inorganic base (KF or Cs₂CO₃) and a small amount of water is crucial in obtaining good performance in the present transition-metal-free reaction.

Key words

transition-metal-free - C-C bond formation - aryl- and vinylboronic acids

References and Notes

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9

We also tested the reactivity of other organoboronic acid derivatives. Potassium 4-methoxyphenyltrifluoroborate was able to react with 1a, but the yield was low (25%). Pinacol ester of 1a did not work as a substrate.

10

The use of Cs₂CO₃ in the absence of H₂O gave 3aa in a moderate yield (60%).

11

In the general conditions, phenylboronic acid (1h) gave the cross-coupling product 3ha in a poor yield (7% yield), and the reaction of 4-acetylphenylboronic acid with 2a did not give the corresponding product.

15

Typical Procedure for a Transition-Metal-Free Cross-Coupling Reaction of Allylic Bromides with Aryl- and Vinylboronic Acids: A mixture of 4-benzyloxyphenyl boronic acid (1d; 0.65 mmol, 1.3 equiv), cinnamyl bromide (2a; 0.5 mmol), and Cs₂CO₃ (0.75 mmol, 1.5 equiv) in CH₂Cl₂-H₂O (1.65 mL, 10:1) was stirred at 60 ˚C for 18 h. After the reaction was completed, the reaction mixture was treated with aq 1 N HCl, extracted with CH₂Cl₂ and dried over MgSO₄. The organic layer was concentrated and the resulting residue was purified by column chromatography on silica gel (hexane-EtOAc, 100:1) to give (E)-3-(4-benzyloxyphenyl)-1-phenyl-1-propene (3da) as a white solid in 91% yield (136.6 mg, 0.455 mmol); mp 44-48 ˚C. ^¹H NMR (500 MHz, CDCl₃): δ = 3.49 (d, J = 6.9 Hz, 2 H), 5.05 (s, 2 H), 6.34 (dt, J = 15.6, 6.9 Hz, 1 H), 6.43 (d, J = 15.6 Hz, 1 H), 6.93 (d, J = 8.7 Hz, 2 H), 7.16 (d, J = 8.7 Hz, 2 H), 7.20 (t, J = 7.4 Hz, 1 H), 7.27-7.39 (m, 7 H), 7.43 (d, J = 6.9 Hz, 2 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 38.6, 70.2, 115.0, 126.2, 127.2, 127.6, 128.0, 128.6, 128.7, 129.7 (two peaks overlap), 130.9, 133.0, 137.3, 137.6, 157.4. IR (neat): 3031, 1454, 1231 cm^-¹. HRMS (EI): m/z [M]⁺ calcd for C₂₂H₂₀O: 300.1514; found: 300.1512.