Room-Temperature Palladium-Catalyzed Allyl Cross-Coupling Reaction with Boronic Acids Using Phosphine-Free Hydrazone Ligands

Abstract

Palladium-catalyzed allyl cross-coupling reaction of allylic acetates with a variety of boronic acids at room temperature using a catalytic amount of Pd(OAc)₂ with phosphine-free hydrazone as a ligand gave the allylbenzene derivatives in good yields.

palladium - catalysis - allyl cross-coupling - boronic ­acid - hydrazones

References and Notes

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General Procedure for Allyl Cross-Coupling Reaction of Cinnamyl and Allyl Acetate with Boronic Acids (Table 2): To a mixture of acetate (0.5 mmol), K₂CO₃ (138.2 mg, 1.0 mmol), Pd(OAc)₂ (2.24 mg, 0.01 mmol), and ligand 1c (2.22 mg, 0.01 mmol) in DMF (1.5 mL) and H₂O (0.5 mL) was added boronic acid (0.6 mmol) at r.t. under an atmosphere of argon. After 1 h, the mixture was diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The residue was purified by silica gel chromatography. All prepared compounds 3 (except for 3e) were known and identified by ^¹H NMR, ^¹³C NMR, and MS. Analytical Data of 3e (Table 2, entry 7): colorless oil. IR (neat): 1604 cm^-¹. ^¹H NMR (CDCl₃): δ = 2.29 (s, 6 H), 3.47 (d, J = 6.5 Hz, 2 H), 6.33 (dt, J = 15.7, 6.6 Hz, 1 H), 6.45 (d, J = 15.9 Hz, 1 H), 6.86 (s, 3 H), 7.16-7.37 (m, 5 H). ^¹³C NMR (CDCl₃):
δ = 21.1, 39.2, 126.1, 126.4, 127.0, 127.8, 128.5, 129.4, 130.8, 137.5, 138.0, 140.0. MS (EI, relative intensity): m/z = 222 (86) [M⁺]. HRMS (FAB-MS): m/z calcd for C₁₇H₁₈: 222.1409; found: 222.1408. GC-MS purity: 98.5%.

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Preparation of Hydrazone 2b: To a solution of N-aminopiperidine (0.060 g, 0.60 mmol) in MeOH (2.0 mL) was added 2-pyridinecarboxaldehyde (0.054 g, 0.51 mmol) and the mixture was stirred for 24 h at r.t. The mixture was directly concentrated under reduced pressure. The residue was purified by silica gel chromatography (hexane-EtOAc, 4:1). Yield: 0.092 g, 0.49 mmol, 96%; colorless oil. IR (neat): 1572 cm^-¹. ^¹H NMR (CDCl₃): δ = 1.51-1.59 (m, 2 H), 1.66-1.79 (m, 4 H), 3.24 (t, J = 5.6 Hz, 4 H), 7.08-7.12 (m, 1 H), 7.59-7.64 (m, 2 H), 7.83 (dd, J = 8.1, 0.8 Hz, 1 H), 8.50 (dd, J = 4.8, 0.8 Hz, 1 H). ^¹³C NMR (CDCl₃): δ = 24.4, 25.4, 52.0, 119.4, 122.3, 134.3, 136.5, 149.4, 156.3. MS (EI, relative intensity): m/z = 189 (11) [M⁺]. HRMS (FAB-MS): m/z calcd for C₁₁H₁₅N₃: 189.1266; found: 189.1280.

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General Procedure for Allyl Cross-Coupling Reaction of Disubstituted Allylic Acetates with 1-Naphthalene- boronic Acid (Table 3): To a mixture of acetate (0.5 mmol), Cs₂CO₃ (423.6 mg, 1.3 mmol), Pd(OAc)₂ (5.61 mg, 0.025 mmol), and ligand 2a (5.08 mg, 0.025 mmol) in MeCN (2 mL) was added 1-naphthaleneboronic acid (103.2 mg, 0.6 mmol) at r.t. under an atmosphere of argon. After 24 h, the mixture was diluted with EtOAc and H₂O. The organic layer was washed with brine, dried over MgSO₄, and concentrated under reduced pressure. The residue was purified by silica gel chromatography. Compounds 3m and 3n were known and identified by ^¹H NMR, ^¹³C NMR, and MS.

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