166330-10-5

(OXYDI-2,1-PHENYLENE)BIS(DIPHENYLPHOSPHINE) can be prepared by a one-step reaction of diphenyl ether and diphenylphosphine chloride.

(1) Dilute diphenyl ether (0.02 mol) in hexane (50 mL), add n-BuLi (42 mmol) in hexane solution dropwise at -78 °C (addition completed within about 5 min), react for 1 h, then raise to room temperature (about 25 °C), and continue stirring for 16 h;
(2) Then, 15 mL of a hexane solution of diphenylphosphine chloride (42 mmol) was added dropwise to the reaction system of step (1) under an ice-water bath (the addition was completed within about 5 min), and the reaction was continued to be stirred at room temperature (about 25 °C) for 16 h. The solvent was removed by rotary evaporation, and a pale yellow viscous oily substance was obtained. After washing with acetone and vacuum drying, 9.4 g of white powder was obtained, which was bis(2-diphenylphosphine) ether: yield 87%, 1H NMR (400 MHz, C6D6) δ: 7.41-7.26 (m, 8H, o-PPh2), 7.08-6.93 (m, 14H, m-PPh2, p-PPh2, phenylate), 6.91-6.87 (t, J＝8Hz, 2H, phenylate), 6.72-6.66 (m, 4H, phenylate) ppm.

1. Useful as a ligand in the Pd-catalyzed formation of diaryl amines.
2. Has been recently applied to the C3 benzylation of indoles.
3. Has been recently applied to the monoallylation of ammonia.
4. Ligand used in the palladium-catalyzed, aerobic oxidation coupling of acyl chlorides with arylboronic acids.
5. Ligand used in carbonylation of aryl iodides.
6. Ligand used in the direct C-H arylation of benzothiodiazoles.
7. Ligand used in stereo-retentive azacyclization of propargylic carbonates.
8. Ligand used in palladium catalyzed benzyne trimerization.