Highly Efficient C-O Cross-Coupling Reactions with Unactivated Halides by Ligandless, Heterogeneous Raney Ni-Al Alloy/Copper (I) Salts

Abstract

A general, novel, ligandless and efficient method was developed for the Raney Ni-Al alloy/copper co-catalyzed formation of diaryl ethers by C-O cross-coupling reaction from aryl iodides, bromides, and even aryl chlorides with phenols.

Key words

copper - Raney Ni-Al alloy - cross-coupling - phenols - ligandless

References

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13

Typical Experimental Procedure. An oven-dried resealable Schlenk tube was fitted with a rubber septum and was cooled to room temperature under N₂ purge. The septum was removed, and the tube was charged with CuI (10 mol%), 10-50 mg Raney Ni-Al alloy, K₂CO₃ (2.0 mmol), aryl halides (1.0mmol), and phenols (1.2-1.4 mmol). The tube was capped with the septum and purged with N₂, and then dioxane(2ml) was added through the septum. The reaction mixture was stirred at 110 °C for 12-24 h (reaction times were not optimized). The reaction mixture was allowed to cool to room temperature and then diluted with ether and poured into a separating funnel. The mixture was washed with 1 M NaOH and brine, and then the organic fraction was dried over anhydrous magnesium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography on silical gel.

17

All the products were identified by NMR and GC-MS (Agilent 6890N GC/5973N MS, HP-5MS). Selected data for the product of entry 13: ¹H NMR (300 MHz, CDCl₃): 7.86 (d, J = 8.7 Hz, 2 H), 7.41-6.92 (18 H), 6.81 (d, J = 8.4 Hz, 2 H); ¹³C NMR (300 MHz, CDCl₃): 157.45, 152.54, 134.19, 129.705, 129.58, 129.26, 128.01, 126.55, 125.75, 124.59, 123.19, 122.64, 119.27, 118.88.