Diverse Pathways for the Palladium(II) Mediated Oxidation of Olefins by t-butylhydroperoxide. Jin-Quan Yu and E. J. Corey*

Transcription

1 Diverse Pathways for the Palladium(II) Mediated xidation of lefins by tylhydroperoxide Jin-Quan Yu and E. J. Corey* Department of Chemistry and Chemical Biology Harvard University, 12 xford Street, Cambridge, Massachusetts Supplementary Information trans-stilbene xide. Into an oven-dried 25 ml two-neck flask equipped with a stir bar was placed Pd(Ac) 2 (3.6 mg, mmol) and CH 2 Cl 2 (2 ml) under N 2. The mixture was cooled to 0 C and t-butylhydroperoxide (TBHP) (160 ul, 1.6 mmol) and K 2 C 3 (11 mg, 0.08 mol) were added. The resulting yellow solution was stirred at 0 C for 0.5 h and BINAP (10.0 mg, mmol) and trans-stilbene (50 ul, 0.32 mmol) were added. The resulting mixture was stirred at 23 C, becoming a cloudy red-brown solution within 1 h. The reaction was shown to be complete in 48 h by TLC analysis. The reaction mixture was filtered through a short pad of silica gel and washed with CH 2 Cl 2. After removal of the solvent by rota evaporation the crude mixture was purified by flash column chromatography using 1:100 ethylacetate:hexane as the eluent to provide 44 mg (70%) of trans-stilbene oxide as a colorless solid. m.p. 69 C; 1 H NMR (600 MHz, CDCl 3 ): δ 7.41 (m, 10 H), 3.90 (s, 2 H). The physical data were in full accordance with those reported in the literature; see Aggarwal, V. K.; Kalomiri, M; Thomas, A. P. Tetrahedron: Asymmetry 1994, 5,

2 3,4-Epoxycyclohexene. Into an oven-dried 25 ml two-neck flask equipped with a stir bar was placed Pd(Ac) 2 (3.6 mg, mmol) and CH 2 Cl 2 (2 ml) under N 2. The mixture was cooled to 0 C, and TBHP (160 ul, 1.6 mmol), K 2 C 3 (11 mg, 0.08 mol) and cyclohexadiene (31 ul, 0.32 mmol) were added. The resulting mixture was stirred for 48 h and then filtered through a short pad of silica gel and washed with CH 2 Cl 2. After removal of the solvent by rota evaporation at 0 C the crude mixture was purified by flash column chromatography using 1:100 ether:hexane as the eluent to provide 28 mg (90%) of 3,4-epoxycyclohexene as an colorless oil. 1 H NMR (600 MHz, CDCl 3 ): δ 5.94 (m, 2 H), 3.50 (m, 1 H), 3.23 (m, 1 H), 2.25 (m, 1H), 2.05 (m, 2 H), 1.60 (m, 1 H); 13 C NMR (400 MHz, CDCl 3 ): 133.5, 123.1, 55.6, 47.5, 20.8, The physical data were in full accordance with those reported in the literature; see Ramesh, K.; Wolfe, M. S.; Lee, Y.; Velde, D. V.; Borchardt, R. T. J. rg. Chem. 1992, 57, Pd(Ac) 2, TBHP K 2 C 3, CH 2 Cl 2, 0 C, 72 h 3-tylperoxy-1-phenylcyclohexene. To an oven-dried 25 ml two-neck flask equipped with a stir bar was placed Pd(Ac) 2 (1.8 mg, mmol), and CH 2 Cl 2 (2 ml) under N 2 at 0 C followed by t-butylhydroperoxide (TBHP) (160 ul, 1.6 mmol) and K 2 C 3 (11.0 mg, 0.08 mol). The mixture was stirred for 1 h and 1-phenylcyclohexene (51 ul, 0.32 mmol) was added. The resulting mixture was stirred vigorously and turned into a brown-orange solution within 1 h. The reaction was monitored by GC and was shown to be 95% complete after 72 h. The reaction mixture was filtered through a short pad of silica gel and washed with CH 2 Cl 2. After removal of the solvent by rota evaporation the crude was purified by flash column chromatography using 1:99 ethyl acetate:hexane as the eluent to provide 49.2 mg (62%) of 3-t-butylperoxy-1- phenylcyclohexene as a clear liquid. 1 H NMR (500 MHz, CDCl 3 ): δ 7.45 (d, J = 8.6 Hz, 2 H), 7.36 (t, J = 8.6 Hz, 2 H), 7.30 (d, J = 8.6 Hz, 1 H), 6.18 (m, 1 H), 4.62 (m, 1 H), 2.50 (m, 1 H), 2.38 (m, 1 H), 2.02 (m, 1 H), 1.92 (m, 1 H), 1.76 (m, 2 H), 1.30 (s, 9 H); 13 C NMR (400 Hz, 2

3 CDCl 3 ): δ 143.1, 141.9, 128.5, 127.7, 125.7, 121.5, 94.8, 80.2, 28.1, 26.8, 26.8, IR (film): 2976, 2933, 1494,, 1446, 1362, 1198, 1074, 967, 884, 757, 695 cm -1. HRMS (EI): calcd for C 16 H 21 2 [M H] + : Found: Pd(Ac) 2, TBHP K 2 C 3, CH 2 Cl 2, 0 C, 72 h 3-tylperoxy-1-t-butylcyclohexene. To an oven-dried 25 ml two-neck flask equipped with a stir bar was placed Pd(Ac) 2 (1.8 mg, mmol) and CH 2 Cl 2 (2 ml) under N 2 at 0 C, followed by TBHP (160 ul, 1.6 mmol) and K 2 C 3 (11.0 mg, 0.08 mol). The mixture was stirred for 1 h and 1-t-butylcyclohexene (54 ul, 0.32 mmol) was added. The resulting mixture stirred vigorously for 72 h (95% complete by GC). The reaction mixture was filtered through a short pad of silica gel and washed with CH 2 Cl 2. After removal of the solvent by rota evaporation, the crude product was purified by flash column chromatography using 1:99 ethyl acetate:hexane as the eluent to provide 49.0 mg (68%) of 3-t-butylperoxy-1-t-butylcyclohexene as a colorless liquid: 1 H NMR (500 MHz, CDCl 3 ): δ 5.55 (m, 1 H), 4.47 (m, 1 H), 2.10 (m, 1 H), 1.96 (m, 1 H), 1.88 (m, 1 H), 1.69 (m, 1 H), 1.58 (m, 1 H), 1.28 (s, 9 H), 1.06 (s, 9 H); 13 C NMR (400 Hz, CDCl 3 ): δ 153.0, 115.6, 80.0, 78.0, 35.9, 29.1, 27.2, 26.8, 25.2, IR (film): 2968, 2869, 1477, 1362, 1248, 1199, 1076, 969 cm -1. HRMS (EI): calcd for C 14 H 26 2 [M] + : Found: Pd(Ac) 2, BINAP, TBHP K 2 C 3, CH 2 Cl 2, 0 C, 72 h 3-tylperoxycyclohexene. Into an oven-dried 25 ml two-neck flask equipped with a stir bar was placed Pd(Ac) 2 (7.2 mg, mmol), CH 2 Cl 2 (2 ml), TBHP (160 ul, 1.6 mmol) and K 2 C 3 (11.0 mg, 0.08 mol) under N 2. The resulting yellow solution was stirred at 0 C for 0.5 h and treated with BINAP (10.0 mg, mmol) and cyclohexene (33 ul, 0.32 mmol). The resulting mixture was stirred and monitored by GC. After 72 h the reaction mixture was filtered through a short pad of silica gel and washed with CH 2 Cl 2. After removal of the solvent by rota 3

4 evaporation at -5 C the crude product was purified by flash column chromatography using 5:95 ether:pentane as the eluent to provide 38.6 mg (71%) of 1-t-butylperoxy-2-cyclohexene as a colorless liquid: 1 H NMR (500 MHz, CDCl 3 ): δ 5.96 (m, 1 H), 5.76 (m, 1 H), 4.41 (m, 1H), ), 2.07 (m, 1 H), 1.96 (m, 2 H), 1.73 (m, 2 H), 1.57 (m, 1 H), 1.26 (s, 9 H); 13 C NMR (400 Hz, CDCl 3 ): δ 133.8, 124.6, 80.1, 76.6, 27.1, 26.7, 25.6, IR (film): 2978, 2934, 1414, 1364, 1198, 1076, 1026, 954 cm -1. HRMS (EI): calcd for C 10 H 18 2 [M] + : Found: Al/Hg, Ehter/H 2 23 C, 1 h H 3-enyl-2-cyclohexen-1-ol. Into a 25 ml round bottom flask equipped with a stir bar was placed a solution of the allylic peroxy ether (123 mg, 0.5 mmol) in 5 ml ether. Freshly prepared amalgam from aluminum foil (0.5 g) and 2% HgCl 2 solution was washed with water, ethanol, ether, and quickly added to the stirred solution along with water (50 ul). The reaction which was exothermic was shown to be complete by TLC after 1 h. The resulting slurry was filtered through a short pad of Celite and washed with 20 ml of ethyl acetate. Removal of the solvent by rota evaporation gives 85.3 mg (98%) of 3-phenyl-2-cyclohexen-1-ol as a white solid: 1 H NMR (500 MHz, CDCl 3 ): δ 7.41 (d, J = 7.0 Hz, 2 H), 7.32 (t, J = 7.0 Hz, 2 H), 7.28 (t, J = 7.0 Hz, 1 H), 6.12 (bs, 1 H), 4.40 (bs, 1 H), 2.48 (m, 1H), 2.38 (m, 1H), 1.95 (m, 1 H), 1.89 (m, 1H), 1.76 (m, 1 H), 1.68 (m, 1H); 13 C NMR (400 Hz, CDCl 3 ): δ 141.5, 140.1, 128.3, 127.4, 126.5, 125.4, 66.3, 31.7, 27.5, The data were in full accordance with those reported in literature; see Hansson, S.; Heumann, A.; Rein, T.; Akermark, B. J. rg. Chem. 1990, 55, 975. Pd/C, TBHP, K 2 C 3 CH 2 Cl 2, 0 C, 12 h 3-enyl-2-cyclopenten-1-one. Into an oven-dried 25 ml two-neck flask equipped with a stir 4

5 K 2 C 3 (11.0 mg, 0.08 mol), and 3-phenylcyclopentene (51 ul, 0.32 mmol) under N 2. The mixture was kept under vigorous stirring at 0 C. Reaction was monitored by TLC and starting material shown to be consumed after 12 h. The reaction mixture was then further stirred for 3 h at 23 C and filtered through a short pad of silica gel washing with CH 2 Cl 2. After removal of the solvent by rota evaporation at 0 0 C the crude product was purified by flash column chromatography using 1:1 ether:hexane as the eluent to provide 36 mg (71%) of 3-phenyl-2- cyclopenten-1-one as a clear liquid: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 5 H), 6.58 (t, J = 1.7 Hz, 1 H), 3.06 (m, 2 H), 2.60 (m, 2 H). 13 C NMR (400 Hz, CDCl 3 ): δ 209.3, 174.0, 134.1, 131.3, 128.9, 127.5, 126.8, 35.3, The physical data were in full accordance with those reported in the literature; see Howell, J. A. S.; Leary, P. J.; Yates, P. C. Tetrahedron 1995, 51, Pd/C, TBHP, K 2 C 3 CH 2 Cl 2, 23 C, 3 h 3-enyl-2-cyclopenten-1-one. Into an oven-dried 25 ml two-neck flask equipped with a stir K 2 C 3 (11.0 mg, 0.08 mol), and 3-t-butylperoxy-1-phenylcyclopentene (74 mg, 0.32 mmol) under N 2. The mixture was stirred vigourously at 23 C and monitored by TLC. After 3 h, the reaction mixture was filtered through a short pad of silica gel, washing with CH 2 Cl 2. After removal of the solvent by rota evaporation at 0 C the crude product was purified by flash column chromatography using 1:1 ether:hexane as the eluent to provide 44 mg (86%) of 3- phenyl-2-cyclopenten-1-one as a clear liquid: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 5 H), 6.58 (t, J = 1.7 Hz, 1 H), 3.06 (m, 2 H), 2.60 (m, 2 H). 13 C NMR (400 Hz, CDCl 3 ): δ 209.3, 174.0, 134.1, 131.3, 128.9, 127.5, 126.8, 35.3, The physical data were in full accordance with those reported in the literature; see Howell, J. A. S.; Leary, P. J.; Yates, P. C. Tetrahedron 1995, 51,

6 Pd/C, TBHP, K 2 C 3 CH 2 Cl 2, 0 C, 12 h 3-enyl-2-cyclohexen-1-one. Into an oven-dried 25 ml two-neck flask equipped with a stir K 2 C 3 (11.0 mg, 0.08 mol), and 1-phenylcyclohexene (51 ul, 0.32 mmol) under N 2. The mixture was stirred at 0 C and monitored by TLC until starting material had been consumed (12 h). The reaction mixture was then further stirred for 3 h at 23 C and filtered through a short pad of silica gel washing with CH 2 Cl 2. After removal of the solvent by rota evaporation at 0 C the crude was purified by flash column chromatography using 1:1 ether:hexane as the eluent to provide 41 mg (75%) of 3-phenyl-2-cyclohexen-1-one as a clear liquid: 1 H NMR (500 MHz, CDCl 3 ): δ (m, 5 H, ArH), 6.42 (s, 1 H), 2.79 (t, J = 6.2 Hz, 2 H), 2.50 (t, J = 6.3 Hz, 2 H), 2.18 (m, 2 H); 13 C NMR (400 Hz, CDCl 3 ): δ 220.1, 159.9, 138.8, 130.0, 128.8, 126.1, 125.5, 37.2, 28.1, The physical data were in full accordance with those reported in the literature; see Guthrie, J. P.; Guo, J. J. Am. Chem. Soc. 1996, 118, Pd/C, TBHP, K 2 C 3 CH 2 Cl 2, 0 C, 12 h 3-tyl-2-cyclohexen-1-one. Into an oven-dried 25 ml two-neck flask equipped with a stir K 2 C 3 (11.0 mg, 0.08 mol), and 1-t-butylcyclohexene (54 ul, 0.32 mmol) under N 2. The mixture was stirred at 0 C. TLC analysis showed that the starting material had been consumed in 12 h. After removal of the solvent by rota evaporation at 0 0 C the crude product was purified by flash column chromatography using 1:1 ether:hexane as the eluent to provide 41 mg (85%) of 3-t-butyl-2-cyclohexen-1-one as a clear liquid: 1 H NMR (500 MHz, CDCl 3 ): δ 5.96 (s, 1H), 2.38 (m, 4 H), 1.98 (m, 2 H), 1.12 (s, 9 H); 13 C NMR (400 Hz, CDCl 3 ): δ 200.8, 173.8, 123.1, 37.5, 36.9, 31.9, 29.7, The physical data were in full accordance with those reported in the literature; see Wada, E.; Funakoshi, J.; Kanemasa, S. Bull. Chem. Soc. Jpn. 1992, 65,