Efficient Palladium-catalyzed Coupling Reactions of Aryl Bromides and Chlorides with Phenols

Transcription

1 Efficient Palladium-catalyzed Coupling Reactions of Aryl Bromides and Chlorides with Phenols Tongjie Hu, a Thomas Schulz, b Christian Torborg, b Xiaorong Chen, a Jun Wang, a Matthias Beller b* and Jun Huang a* Experimental section: Reagents: All reagents were purchased from Aladdin Reagent Company and Alfa-Aesar Company without further purification. Toluene and dioxane were purified by distillation though a standard procedure. Analytical Methods: 1 H-NMR and 13 C-NMR spectra were recorded on a Bruker 300 MHz instrument with chemical shifts reported in ppm relative to the residual deuterated solvent or the internal standard tetramethylsilane. Gas chromatography analyses were performed on a Hewlett Packard 5890 instrument with a FID detector and Hewlett Packard 24 m x 0.2 mm i.d. HP-5 capillary column. Yield refers to isolated yields of compounds greater than 95% purity as determined by capillary gas chromatography (GC) and proton Nuclear Magnetic Resonance spectroscopy ( 1 H-NMR) analysis. General procedure for the Pd-catalyzed synthesis of diaryl ethers from aryl halides with phenols. All reactions were carried out under an argon atmosphere in schlenk tubes (containing a stir bar). A schlenk tube containing a stir bar was charged with Pd(OAc) 2 ( mol% Pd), ligand ( mol%) and K 3 PO 4 ( equiv.). If the aryl halides ( mmol) and/or phenols (1.2 equiv.) were solids, they were also added at this time. The tube was evacuated and backfilled with argon (this sequence was repeated three times). If the aryl halides and/or phenols were liquids, they were added to the tube at this time along with the solvents. The mixture was stirred in a preheated oil bath ( C) until the aryl halide was consumed as judged by TLC or GC analysis (10-24 h, reaction times were not optimized). The crude material was purified by column chromatography on silica gel (eluting with ethyl acetate/hexane or diethyl ether/hexane mixtures). 1-(4-Phenoxyphenyl)ethanone 1 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a white solid. M.p. 51 C; 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (t, 2H), (t, 1H), 8-6 (d, 2H), (d, 2H), 2.57 (s, 3H). 4-Phenoxybenzonitrile 2 : The crude material was purified by flash chromatography column on

2 silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a white solid. M.p. 29 C; 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (t, 2H) (t, 1H), 8-5 (d, 2H), (d, 2H). 4-Phenoxybenzaldehyde 3 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow liquid. 1 H NMR (CDCl 3, 300 MHz): 9.92 (s, 1H), (d, 2H), (t, 2H), (q, 1H), 9-4 (t, 4H). 2-Phenoxybenzaldehyde 4 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow liquid. 1 H NMR (CDCl 3, 300 MHz): (s, 1H), (d, 1H), (t, 1H), (t, 2H), (t, 2H), 8-5 (d, 2H), (d, 1H). 1-Methoxy-4-phenoxybenzene 4 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a colorless liquid. 1 H NMR (CDCl 3, 300 MHz): (m, 2H), 7-2 (t, 1H), (m, 4H), (m, 2H), 3.81 (s, 3H). Methyl 4-phenoxybenzoate 5 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow solid. M.p. 59 C; 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (t, 2H), (t, 1H), 7-5 (d, 2H), (d, 2H), 3.89 (s, 3H). 1-(4-(o-Tolyloxy)phenyl)ethanone 6 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow solid. M.p. 35 C; 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (t, 1H), (m, 2H),

3 (d, 1H), (d, 1H), 2.57 (s, 3H), 2.18 (s, 3H). 4-(o-Tolyloxy)benzonitrile 7 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a colorless liquid. 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (t, 1H), (m, 2H), (d, 1H), (d, 2H), 2.17 (s, 3H). 4-(o-Tolyloxy)benzaldehyde 8 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow liquid. 1 H NMR (CDCl 3, 300 MHz): 9.90 (s, 1H), (t, 2H), (t, 1H), (m, 2H), (q, 3H), 2.18(s, 3H). 2-(o-Tolyloxy)benzaldehyde 9 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow solid. M.p. 50 C; 1 H NMR (CDCl 3, 300 MHz): (s, 1H), (d, 1H), (t, 1H), (t, 1H), (t, 1H), (m, 2H), (d, 1H), (d, 1H), 2.19 (s, 3H). Methyl 4-(o-tolyloxy)benzoate 8 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a yellow liquid. 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (m, 2H), (t, 1H), (d, 1H), (d, 2H), 3.89 (s, 3H), 2.19 (s, 3H).

4 1,1`-Oxydinaphthalene 10 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a white solid. M.p. 109 C; 1 H NMR (CDCl 3, 300 MHz): (d, 2H), (d, 2H), (d, 2H), (m, 4H), (t, 2H), (d, 2H). 1-Methoxy-2-phenoxybenzene 11 : The crude material was purified by flash chromatography column on silica gel (10:1 ethyl acetate/hexane) to afford the title compound as a light yellow solid. M.p. 76 C; 1 H-NMR (CDCl 3, 300 MHz): (m, 2H), (m, 1H), (m, 2H), (m, 4H), 3.84 (s, 3H). 1. J. J. Niu, H. Zhou, Z. J. Li, J. W. Xu, S. J. Hu, J. Org. Chem. 2008, 73, Commercially available (Aldrich). 3. J. S. Sawyer, E. A. Schmittling, J. A. Palkowitz, W. J. Smith, J. Org. Chem. 1998, 63, C. H. Burgos, T. E. Barder, X. H. Huang, S. L. Buchwald, Angew. Chem. Int. Ed. 2006, 45, H. E. Ungnade, E. F. Orwell, Organic Synthesis; John Wiley and Sons: New York, 1955; Collect. Vol. 3, pp A. Aranyos, D. W. Old, A. Kiyomori, J. P. Wolfe, J. P. Sadighi, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, S. Harkal, K. Kumar, D. Michalk, A. Zapf, R. Jackstell, F. Rataboul, T. Riermeler, A. Monsees, M. Beller, Tetrahedron Lett. 2005, 46 (18), S. L. Buchwald, D. W. Old, J. P. Wolfe, et. al, PCT Int. Appl., 2000, 397, WO K. Shimizu, K. Kizawa, T. Yoshimoto, J. Imamura, Sekiyu Gakkai shi, 1982, 25, N. R. Biebrich, Ber. Deu. Chem. Ges. 1882, 15, J. Suribabu, S. Sekarpandi, R. Laxmidhar, M. Tathagata, M. Santu, M. Raja, S. Prasenjit, P. Tharmalingam, J. Org. Chem. 2009, 74,

5 HJJ-3 1H-NMR CDCl3 300K AV NAME : EXPNO : 14 DATE_t : 07:13:54 DATE_d : Mar DE : usec INSTRUM : av300 NS : 32 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : 17 ppm Stop : ppm AQ_time : sec

6 HTJ-4 1H-NMR CDCl3 300K AV-300

7 HTJ-9 1H-NMR CDCl3 300K AV NAME : EXPNO : 36 DATE_t : 02:59:03 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec

8 HTJ-8 1H-NMR CDCl3 300K AV NAME : EXPNO : 35 DATE_t : 02:55:22 DATE_d : Mar DE : usec INSTRUM : av300 NS : 1 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec

9 HJJ-2 1H-NMR CDCl3 300K AV NAME : EXPNO : 13 DATE_t : 07:09:58 DATE_d : Mar DE : usec INSTRUM : av300 NS : 32 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm - Stop : ppm AQ_time : sec

10 HTJ-11 H1-NMR CDCl3 300K AV NAME : EXPNO : 63 DATE_t : 01:00:42 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec

11 HTJ-5 1H-NMR CDCl3 300K AV NAME : EXPNO : 32 DATE_t : 02:43:44 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec

12 O NC HTJ-6 1H-NMR CDCl3 300K AV NAME : EXPNO : 33 DATE_t : 02:47:23 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec

13 HTJ-7 1H-NMR CDCl3 300K AV NAME : EXPNO : 34 DATE_t : 02:51:44 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm 1 1 Stop : ppm AQ_time : sec

14 HTJ-10 H1-NMR CDCl3 300K AV NAME : EXPNO : 62 DATE_t : 00:57:24 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm 1 Stop : ppm AQ_time : sec

15 HTJ-12 H1-NMR CDCl3 300K AV NAME : EXPNO : 64 DATE_t : 01:05:43 DATE_d : Mar DE : usec INSTRUM : av300 NS : 16 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : -1 ppm AQ_time : sec

16 HTJ-13 H1-NMR CDCl3 300K AV NAME : EXPNO : 78 DATE_t : 01:56:36 DATE_d : Mar DE : usec INSTRUM : av300 NS : 8 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : LB : 0.10 Hz PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm 1 1 Stop : ppm AQ_time : sec

17 HJJ-1 1H-NMR CDCl3 300K AV NAME : EXPNO : 12 DATE_t : 07:00:44 DATE_d : Mar DE : usec INSTRUM : av300 NS : 32 PULPROG : zg30 SFO1 : MHz SW_h : Hz TD : TE : 29 K GB : PC : 0 PPARMOD : 1D SF : MHz SSB : SW_p : TDeff : XOffset : 0 cm YOffset : 0 cm Start : ppm Stop : ppm AQ_time : sec