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DOI: 10.1055/s-0028-1083381
Room-Temperature Palladium-Catalyzed Allyl Cross-Coupling Reaction with Boronic Acids Using Phosphine-Free Hydrazone Ligands
Publication History
Publication Date:
01 October 2008 (online)
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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.
Key words
palladium - catalysis - allyl cross-coupling - boronic acid - hydrazones
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References and Notes
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%.
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.
18General 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.