Supporting Information for. A convenient Method for Epoxidation of Alkenes using Aqueous. Hydrogen Peroxide

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1 Supporting Information for A convenient Method for Epoxidation of Alkenes using Aqueous Hydrogen Peroxide Man Kin Tse, Markus Klawonn, Santosh Bhor, Christian Döbler, Gopinathan Anilkumar, and Matthias Beller* Leibniz-Institut für Organische Katalyse an der Universität Rostock e.v., Buchbinderstr. 5-6, Rostock, Germany. matthias.beller@ifok.uni-rostock.de Experimental Section General Methods. Starting materials were used as received from Aldrich, Fluka, Acros and Strem. Catalyst 1a was synthesized according to a literature procedure. 1 Synthesis of complex (1b) [Ru( t Bu 3 -tpy)(pydic)]: t Bu 3 -tpy (200 mg, 0.50 mmol) and [Ru(pcymene)Cl 2 ] 2 (152 mg, 0.25 mmol) were dissolved in MeOH (8 ml) at room temperature under Ar to form a dark violet solution. Na 2 pydic (105 mg, 0.50 mmol) was dissolved in MeOH/H 2 O 2:1 (9 ml). It was then purged with Ar for 15 min. and added dropwise to the Ru solution via a cannula. The reaction mixture was heated at 65 C for 1 h. During this time it turned to deep purple in color. It was then cooled at 30 C. A purple crystalline solid formed which was filtered, washed with EtOH (5 ml x 2) and dried under high vacuum to yield Ru( t Bu 3 -tpy)(pydic) (261 mg, 78%). R f = 0.19 (CH 2 Cl 2 /MeOH 100:5). 1 H NMR (400.1 MHz, CDCl 3, ppm) δ 1.36 (s, 18 H), 1.61 (s, 9 H), 7.22 (dd, J = 5.9, 1.8 Hz, 2 H), 7.44 (d, J = 5.9 Hz, 2 H), 8.06 (t, J = 7.8 Hz, 1 H), 8.10 (d, J = 1.8 Hz, 2 H), 8.24 (s, 2 H), 8.37 (d, J = 7.8 Hz, 2 H). FAB-MS m/z 668 (M + ). Uv-vis (CH 2 Cl 2, λ max /nm, log ε) 321 (4.57), 393 (4.10), 524 (4.05). Elementary analysis calcd. C 34 H 38 N 4 O 4 Ru (%) C 61.15, H 5.74, N 8.39; found C 61.09, H 5.65, N 8.46.

2 Synthesis of complex (5) [Ru(tpy-β-pinene)(pydic)]: By using tpy-β-pinene 2 (200 mg, 0.47 mmol), [Ru(p-cymene)Cl 2 ] 2 (145 mg, 0.24 mmol) and Na 2 pydic (100 mg, 0.47 mmol), a purple crystalline solid Ru(tpy-β-pinene)(pydic) (61 mg, 19%) was obtained. R f = 0.20 (CH 2 Cl 2 /MeOH 100:5). 1 H NMR (400.1 MHz, CD 2 Cl 2, ppm) δ 0.44 (s, 6 H), 1.00 (d, J = 9.9 Hz, 2 H), 1.26 (s, 6 H), (m, 2 H), (m, 4 H), (m, 2 H), (m, 2 H), 7.27 (d, J = 7.9 Hz, 2 H), 7.75 (t, J = 8.1 Hz, 1 H), 8.00 (d, J = 7.9 Hz, 2 H), 8.08 (t, J = 7.7 Hz, 1 H), 8.24 (d,, J = 8.1 Hz, 2 H), 8.30 (d,, J = 7.7 Hz, 2 H). 13 C NMR (100.6 MHz, CD 2 Cl 2, ppm) δ 20.6, 24.9, 30.2, 34.2, 38.3, 40.0, 47.1, 119.3, 120.3, 127.6, 130.5, 133.3, 133.8, 145.7, 155.0, 157.8, 158.2, 164.3, FAB-MS m/z 688 (M + ). Uv-vis (CH 2 Cl 2, λ max /nm, log ε) 339 (4.57), 399 (3.95), 524 (3.94) 569 (sh, 3.90). Elementary analysis calcd. C 36 H 34 N 4 O 4 Ru H 2 O (%) C 61.27, H 5.14, N 7.94; found C 61.65, H 5.18, N Synthesis of complex (6) [Ru(tpy-myrt)(pydic)]: By using tpy-myrt 2 (211 mg, 0.50 mmol), [Ru(p-cymene)Cl 2 ] 2 (152 mg, 0.25 mmol) and Na 2 pydic (105 mg, 0.50 mmol), a purple solid Ru(tpy-myrt)(pydic) (300 mg, 90%) was obtained. R f = 0.28 (CH 2 Cl 2 /MeOH 100:5). 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 0.62 (s, 6 H), (m, 2 H), 1.35 (s, 6 H), (m, 2 H), (m, 4 H), (m, 4 H), 7.09 (s, 2 H), 7.76 (t, J = 8.0 Hz, 1 H), 8.05 (s, 2 H), 8.09 (t, J = 7.8 Hz, 1 H), 8.25 (d, J = 8.0 Hz, 2 H), 8.31 (d, J = 7.8 Hz, 2 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 21.1, 25.5, 31.3, 32.8, 38.9, 39.8, 44.9, 119.6, 121.5, 127.3, 129.2, 133.4, 145.0, 146.5, 146.7, 151.1, 157.6, 157.7, 172.1; FAB-MS (E.I., 70 ev) m/z 688 (M + ); Uv-vis (CH 2 Cl 2, λ max /nm, log ε) 332 (4.58), 392 (4.08), 518 (4.01). Elementary analysis calcd. C 36 H 34 N 4 O 4 Ru 0.5CH 2 Cl 2 (%) C 60.04, H 4.83, N 7.67; found C 59.91, H 5.08, N 7.86.

3 Synthesis of complex (7) [Ru(tpy-Me 2 -β-pinene)(pydic)]: tpy-me 2 -β-pinene 2 (50 mg, 0.11 mmol), RuCl 3 xh 2 O (29 mg, 0.11 mmol) were heated at 125 C in n BuOH overnight. The colour of the reaction mixture turned from deep orange to greenish red in 5 min. and violet after overnight heating. H 2 pydic (19 mg, 0.11 mmol) and Et 3 N (46.6 µl, 0.33 mmol) were then added and the reaction mixture was heated for another 1 h at 125 C, during which the colour changed to deep purple. After removal of solvent under reduced pressure, the product was chromatographed on silica gel ( mesh) using 100:2 to 100:5 CH 2 Cl 2 :MeOH as the gradient eluent to give a purple crystalline solid after removal of solvent (41 mg, 57%). Analytical sample was obtained by recrystallization over CH 2 Cl 2 /n-hexane. R f = 0.12 (CH 2 Cl 2 /MeOH 100:5). 1 H NMR (400.1 MHz, CD 2 Cl 2, ppm) δ 0.54 (s, 6 H), 0.60 (d, J = 6.9 Hz, 6 H), 1.17 (d, J = 10.3 Hz, 2 H), 1.32 (s, 6 H), 1.73 (m, 2 H), 1.94 (ddd, J = 13.8, 6.9, 3.6 Hz, 2 H), 2.35 (m, 2 H), 2.70 (m, 2 H), 7.23 (d, J = 7.8 Hz, 2 H), 7.81 (t, J = 8.1 Hz, 1 H), 7.92 (d, J = 7.8 Hz, 2 H), 8.09 (t, J = 7.7 Hz, 1 H), 8.18 (d, J = 8.1 Hz, 2 H), 8.31 (d, J = 7.7 Hz, 2 H). 13 C NMR (100.6 MHz, CD 2 Cl 2, ppm) δ 20.9, 21.1, 25.2, 27.3, 37.9, 40.5, 47.0, 48.1, 119.2, 120.7, 127.2, 131.6, 133.7, 134.1, 144.5, 155.7, 158.6, 159.1, 169.7, FAB- MS m/z 716 (M + ). Uv-vis (CH 2 Cl 2, λ max /nm, log ε) 338 (4.54), 396 (3.94), 522 (3.89). HRMS cald. for (C 38 H 38 N 4 O Ru + H + ) m/z found Synthesis of complex (8) [Ru(tpy-cam)(pydic)]: tpy-cam (crude 137 mg, 0.30 mmol), RuCl. 3 xh 2 O (80 mg, 0.30 mmol) were heated at 125 C in n BuOH overnight. It turned from deep orange to greenish red in 5 min. and violet after overnight heating. H 2 pydic (61 mg, 0.30 mmol) and Et 3 N (128 µl, 0.91 mmol) were then added and the reaction mixture was heated for another 1 h at 125 C, during which the colour changed to deep purple. After removal of solvent under reduced pressure, the product was chromatographed on silica gel ( mesh) using 100:0 to 100:5 CH 2 Cl 2 :MeOH as the gradient eluent to give a purple

4 crystalline solid after removal of solvent (18 mg, 8%). Analytical sample was obtained by recrystallization over CH 2 Cl 2 /n-hexane. R f = 0.18 (CH 2 Cl 2 /MeOH 100:5). 1 H NMR (400.1 MHz, CD 2 Cl 2, ppm) δ 0.35 (s, 6 H), 0.73 (s, 6 H), (m, 2 H), (m, 2 H), 1.21 (s, 6 H), 1.39 (d, J = 3.89 Hz, 2 H), (m, 4 H), 7.38 (d, J = 7.5 Hz, 2 H), 7.73 (t, J = 7.2 Hz, 1 H), 8.07 (d, J = 7.7 Hz, 2 H), 8.12 (t, J = 7.7 Hz, 1 H), 8.22 (d, J = 7.5 Hz, 2 H), 8.34 (d,, J = 7.7 Hz, 2 H). 13 C NMR (100.6 MHz, CD 2 Cl 2, ppm) δ 10.7, 18.1, 19.4, 25.6, 32.3, 52.1, 53.4, 56.3, 119.7, 120.0, 126.5, 127.6, 130.5, 133.1, 148.9, 153.8, 156.3, 157.8, 172.5, FAB-MS m/z 717 (M + H + ). Uv-vis (CH 2 Cl 2, λ max /nm, log ε) 335 (4.49), 386 (3.90), 519 (3.85). HRMS cald. for (C 38 H 38 N 4 O Ru + H + ) m/z found The terpyridine ligands of the corresponding complexes 5, 6 and 7 were prepared according to a literature procedure. 2 Synthesis of tpy-cam-ligand for complex 8: 2-Methylenebornane 3 : In a 250 ml two-necked round bottomed flask flushed with Argon, sodium hydride (1.2 g, 0.06 mmol) was dissolved in DMSO (20 g) by heating to 80 C for half an hour. After cooling to ambient temperature, methyltriphenylphosphonium bromide (17.9 g, 0.05 mmol) in DMSO (50 ml) and camphor (6 g, 0.04 mmol) in DMSO (20 ml) were added. This mixture was then immersed into an oil bath and kept at 60 C for 72 hours. The mixture was poured into a beaker containing water (50 ml) and extracted with n-pentane (50 ml x 3). The combined organic layers were evaporated and subjected to column chromatography (silica gel, n-pentane) to yield colorless crystals (2.12 g, 36 %). mp: C; 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 0.75 (s, 3 H), 0.89 (s, 3 H), 0.91 (s, 3 H), (m, 2 H), (m, 1 H), (m, 2 H), (m, 1H), (m, 1 H), (m, 2 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 12.6, 19.0, 19.7, 28.3, 35.5, 37.3, 45.1, 47.5, 51.8, 101.1, 160.1; [α] D = (CH 2 Cl 2, c = 0.92); MS (E.I., 70 ev): m/z 151 ([M+1] +, 3),

5 150 ([M] +, 25), 135 (54), 121 (28), 108 (21), 107 (100), 95 (37), 94 (52), 93 (61), 91 (48), 79 (68); HRMS cald. for C 11 H 18 m/z found Methylene-3-oxobornane 4 : 2-Methylenebornane (1.89 g, 12.6 mmol) and selenium dioxide (1.4 g, 12.6 mmol) in carbon tetrachloride (5 ml) were heated to reflux for 14 h. The mixture was evaporated to dryness and subjected to column chromatography (silica gel, n- hexane) to yield a pale yellow crystals with a camphor-like smell (873 mg, 42%). mp: C; Rf = 0.4 (n-hexane, silica gel) 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 0.82 (s, 3 H), 0.96 (s, 3 H), 1.09 (s, 3 H), (m, 2 H), 1.86 (dd, J = 10.5 Hz, 1 H), 1.99 (ddd, J = 10.5, 5.2, 2.2 Hz, 1H), 2.20 (d, J = 5.2 Hz, 1 H), 5.01 (s, 1 H), 5.74 (d, J = 0.6 Hz, 1 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 11.9, 17.3, 20.4, 22.7, 34.5, 45.7, 51.6, 59.3, 110.4, 154.7, 255.7; [α] D = (CH 2 Cl 2, c = 0.64); MS (E.I., 70 ev): m/z 165 ([M+1] +, 9), 164 ([M] +, 63), 149 (56), 136 (21), 122 (28), 121 (100), 107 (33), 96 (65), 95 (48), 93 (66), 91 (34), 79 (38), 77 (32), 69 (35), 67 (82), 55 (32), 41 (93), 39 (49), 27 (40). HRMS cald. for (C 11 H 16 O) m/z found cam-tpy ligand for complex 8: 2-Methylene-3-oxobornane (773 mg, 4.71 mmol), ammonium acetate (726 mg, 9.42 mmol) and 2,6-Bis(pyridinoacetyl)pyridine diiodide 2a (1.347 g, 2.35 mmol) were suspended in acetic acid (10 ml) and heated to 120 C in a pressure tube for 14 hours. Then, the mixture was neutralized by sodium carbonate solution (prepared by dissolving 30 g Na 2 CO H 2 O in 150 ml water) and extracted by chloroform ( 50 ml x 3). The combined organic layers were dried over K 2 CO 3 and evaporated to give the crude ligand. It was not further purified and used directly in the synthesis of complex 8. General Procedure for the Epoxidation Reaction: In a 25 ml Schlenk tube, the catalyst was stirred at room temperature in tert-amyl alcohol (9 ml) for 10 min. Olefin (0.5 mmol)

6 and dodecane (GC internal standard, 100 µl) were added. To this reaction mixture, a solution of 30% hydrogen peroxide (170 µl, 1.5 mmol) in tert-amyl alcohol (830 µl) was added over a period of 12 h by a syringe pump. The reaction was then quenched by adding water (10 ml) and Na 2 SO 3 (500 mg). The mixture was extracted with ethyl acetate (20 ml) and the organic layer was dried over MgSO 4. From this solution, aliquots were taken and analyzed by GC for yield and conversion data. To isolate the epoxides, the ethyl acetate solution was evaporated to dryness. In most cases the remaining epoxides were pure by 1 H NMR, otherwise further purification (column chromatography, Merck silica gel 60, hexane to hexane/ethyl acetate 95:5 as the gradient eluent) was done. 1,2-Epoxy-1-methylcyclohexane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.22 (m, 5 H), (m, 2 H), 1.59 (m, 2 H), (m, 2 H), 2.87 (s, 1 H); 13 C NMR (100.6 MHz, CDCl 3, ppm): δ 19.7, 20.1, 22.7, 25.0, 29.9, 57.8, 59.6; (E.I., 70 ev): m/z 112 (M + ), 111, 97 (100), 55, 43. Phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 2.72 (dd, J =5.6, 2.6 Hz, 1 H), 3.06 (dd, J = 5.6, 4.2 Hz, 1 H), 3.78 (dd, J = 4.2, 2.6 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 51.3, 52.5, 125.6, 128.3, 128.6, 137.7; (E.I., 70 ev): m/z 120 (M +, 41), 119 (65), 92 (37), 91 (100), 90 (64), 89 (79). 2-(p-Tolyl)-oxirane: 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 2.33 (s, 3 H), 2.77 (dd, J = 5.5, 2.6 Hz, 1 H), 3.09, (dd, J = 5.5, 4.1 Hz, 1 H), 3.79, (dd, J = 4.1, 2.6 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 20.9, 50.9, 52.1, 125.5, 129.2, 134.8, 138.1; GC-MS: m/z 134 (M + ).

7 4-Fluorophenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 2.67 (dd, J = 5.6, 2.6 Hz, 1 H), 3.04 (dd, J = 5.6, 4.0 Hz, 1 H), 3.75 (dd, J = 4.0, 2.6 Hz, 1 H), (m, 2 H), (m, 2H), 13 C NMR (100.6 MHz, CDCl 3 ): δ 51.6, 52.2, (d, J = 20 Hz), (d, J = 7 Hz), (d, J = 2 Hz), (d, J = 24 Hz); (E.I., 70 ev): m/z 138 (M + ), 137 (M-1 + ), 122 (86), 109 (100), Chlorophenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 2.68 (dd, J = 5.6, 2.6 Hz, 1 H), 3.07 (dd, J = 5.6, 4.0 Hz, 1 H), 3.76 (dd, J = 4.0, 2.6 Hz, 1 H), (m, 4 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 51.4, 51.9, 127.0, 128.8, 134.1, 136.3; (E.I., 70 ev): m/z 156 (M+2 +, 9), 155 (M+1 +, 10), 154 (M +, 28), 153 (M-1 +, 23), 125 (53), 119 (74), 89 (106). (4-Trifluoromethyl)phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 2.77 (dd, J = 5.6, 2.6 Hz, 1 H), 3.19 (dd, J = 5.6, 4.0 Hz, 1 H), 3.92 (dd, J = 4.0, 2.6 Hz, 1 H), 7.4 (d, J = 8.1 Hz, 2 H), 7.6 (d, J = 8.1 Hz, 2 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 51.4, 51.6, (q, J = 3.8 Hz), 125.9, 141.9; (E.I., 70 ev): m/z 188 (M +, 14), 187 (20), 159 (49), 158 (48), 119 (100), 91 (37). trans-2-methyl-3-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.44 (d, J = 5.2 Hz, 3 H), 3.03 (dq, J = 5.2, 2.0 Hz, 1 H), 3.57 (d, J = 2.0 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 18.0, 59.2, 59.6, 125.7, 128.1, 128.5, 137.9; (E.I., 70 ev): m/z 134 (M +, 52), 133 (65), 105 (51), 91 (42), 90 (100), 89 (77), 77 (23). cis-β-methylstyrene oxide: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.07 (d, J = 5.4 Hz, 3 H), 3.33 (dd, J = 5.4, 4.3 Hz, 1 H), 4.05 (d, J = 4.3 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 12.5, 55.1, 57.5, 126.5, 127.4, 128.0, 135.5; MS (E.I., 70 ev): m/z 134 (M + ).

8 1,2-Dihydronaphthalene oxide: 1 H NMR (400.1 MHz, CDCl 3 ): δ (m, 1 H), 2.41 (dddd, J = 14.5, 6.5, 2.9, 1.7 Hz, 1 H), 2.55 (dd, J = 15.5, 5.6 Hz, 1 H), (m, 1 H), (m, 1 H), 3.85 (d, J = 4.4 Hz, 1 H), 7.10 (d, J = 7.3 Hz, 1 H), (m, 1 H), (m, 1 H), 7.40 (dd, J = 7.3, 1.4 Hz, 1 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 21.7, 24.3, 52.6, 54.9, 126.0, 128.2, 128.3, 129.4, 132.4, 136.5; GC-MS: m/z 146 (M + ). 2-Methyl-2-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.65 (s, 3 H), 2.73 (d, J = 5.4 Hz, 1 H), 2.90 (d, J = 5.4 Hz, 1 H), (m, 5 H), 13 C NMR (100.6 MHz, CDCl 3 ): δ 56.9, 57.2, 125.4, 127.6, 128.5, 141.3; MS (E.I., 70 ev): m/z 134 ([M] +, 35), 133 (87), 105 (100), 104 (41), 103 (58), 91 (23), 79 (37), 78 (54), 77 (49). 2,2-Dimethyl-3-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.04 (s, 3 H), 1.45 (s, 3 H), 3.83 (s, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 17.9, 24.7, 61.0, 64.5, 126.3, 127.3, 128, 136.6; MS (E.I., 70 ev) m/z 148 (M + ). 1,2-epoxy-1-phenyl-cyclohexane: 1 H NMR (400.1 MHz, CDCl 3 ): δ (m, 1 H), (m, 1 H), (m, 2 H), (m, 2 H), (m, 1 H), (m, 1 H), 2.99 (m, 1 H), (m, 1 H), (m, 4 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 19.9, 20.2, 24.8, 29.0, 60.3, 62.1, 125.4, 127.3, 128.4, 142.6, MS (E.I., 70 ev): m/z = 175 ([M+1] +, 10), 174 ([M] +, 82), 173 (100), 159 (21), 145 (40), 129 (50), 117 (47), 115 (58), 105 (68), 91 (58), 77 (43).

9 2-Phenyl-1-oxaspiro[2.5]octane: 1 H NMR (400.1 MHz, CDCl 3 ): δ (m, 2 H), (m, 8 H), 3.85 (s, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 24.5, 25.3, 25.5, 28.4, 35.4, 64.5, 65.5, 126.3, 127.2, 127.9, 136.3; MS (E.I., 70 ev) m/z 188 (M + ). 2-Methyl-2,3-diphenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.48 (s, 3 H), 3.98 (s, 1 H), (m, 2 H), (m, 6 H), (m, 2 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 16.7, 63.0, 67.1, 125.1, 126.5, 127.5, 127.6, 128.2, 128.4, 135.9, 142.3; MS (E.I., 70 ev): m/z 210 (M + ). Triphenylethyleneoxide: 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 4.39 (s, 1 H), (m, 15 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 68.0; 69.0, 126.7, 127.1, 127.8, 127.9, 128.0, 128.1, 128.2, 128.7, 129.4, 135.9, 136.4, 141.4; MS (E.I., 70 ev): m/z = 273 (M + +1, 3), 272 (M +, 15), 243 (41), 167 (22), 166 (41), 165 (100), 105 (55). 2-Methylindene oxide: 1 H NMR (400.1 MHz, CDCl 3 ): δ 1.69 (s, 3 H), 2.90 (d, J = 17.7 Hz, 1 H), 3.15 (d, J = 17.7 Hz, 1 H), 4.04 (d, J = 1.2 Hz, 1 H), (m, 3 H), 7.44 (d, J = 7.3 Hz, 1 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 18.5, 38.6, 65.0, 65.3, 124.8, 125.7, 126.0, 128.2, 141.7, 144.5; MS (E.I., 70 ev) m/z 146 (M + ). 2,2,3-Trimethyl-3-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 0.95 (s, 3 H), 1.46 (s, 3 H), 1.61 (s, 3 H), (m, 1 H), (m, 4 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 20.7, 21.3, 21.7, 63.7, 66.5, 126.0, 126.7, 128.0, 142.2; MS (E.I., 70 ev) m/z 162 (M + ). trans-2-hydroxymethyl-3-phenyloxirane: 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 1.84 (br s, 1 H), 3.20 (d, J = 4.2, 2.2 Hz, 1 H), 3.74 (dd, J = 12.7, 4.2 Hz, 1 H), 3.88 (d, J = 2.2 Hz, 1 H),

10 4.01 (dd, J = 12.7, 2.2 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 55.8, 61.7, 62.8, 116.7, 126.1, 128.5, 128.8; MS (E.I., 70 ev): m/z 150 ([M] +, 5), 132 (19), 131 (12), 119 (19), 107 (100), 105 (33), 104 (34), 91 (67), 90 (78), 89 (58), 79 (67), 77 (41). trans-2-[(tert-butyldimethylsiloxy)methyl]-3-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 0.09 (s, 3 H), 0.10 (s, 3 H), 0.91 (s, 9 H), (ddd, J = 4.4, 2.8, 1.9 Hz, 1 H), 3.79 (d, J = 1.9 Hz, 1 H), 3.81 (dd, J = 12.0, 4.4 Hz, 1 H), 3.95 (dd, J = 12.0, 2.8 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ -5.3, 18.4, 25.9, 55.9, 62.7, 64.0, 125.7, 128.1, 128.4, 137.2; MS (E.I., 70 ev): m/z 249 (M + - CH 3 ). 3-Phenyloxiranylmethyl acetate: 1 H NMR (400.1 MHz, CDCl 3 ): δ 2.04 (s, 3 H), (m, 1 H), 3.73 (d, J = 2.0 Hz, 1 H), 4.02 (dd, J = 12.3, 6.0 Hz, 1 H), 4.41 (dd, J = 12.3, 3.4 Hz, 1 H), (m, 5 H), 13 C NMR (100.6 MHz, CDCl 3 ): δ 20.7, 56.4, 59.2, 64.2, 125.6, 128.4, 128.5, 136.1, 170.7; MS (E.I., 70 ev): m/z 192 (M +, 2), 150 (10), 149 (79), 133 (26), 107 (95), 105 (67), 91 (54), 90 (45), 89 (42), 79 (31), 77 (31), 43 (100). trans-2-methoxymethyl-3-phenyloxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 3.19 (ddd, J = 5.2, 3.1, 2.1 Hz, 1 H), 3.43 (s, 3 H), 3.52 (dd, J = 11.4, 5.2 Hz, 1 H), 3.76 (dd, J = 11.4, 3.1 Hz, 1 H), 3.78 (d, J = 2.1 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 55.7, 59.2, 60.9, 72.1, 125.6, 128.2, 128.4, 136.8; MS (E.I., 70 ev) m/z 164 (M + ). trans-2-(p-methoxyphenyl)-3-methyloxirane: 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 1.41 (d, J = 5.2 Hz, 3 H), 3.01 (qd, J = 5.2, 2.0 Hz, 1 H), 3.50 (d, J = 2.0 Hz, 1 H), 3.79 (s, 3 H), 6.87 (d, J = 8.9 Hz, 2 H), 7.17 (d, J = 8.9 Hz, 2 H); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 18.0, 58.9,

11 59.5, 114.1, 127.2, 130.3, 160.0; MS (E.I., 70 ev): m/z = 165 ([M+1] +, 7), 164 (M +, 57), 121 (47), 120 (82), 105 (31), 91 (100), 77 (55), 51 (37). trans-2-phenoxymethyl-3-phenyl-oxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 3.40 (ddd, J = 5.2, 3.2, 2.0 Hz, 1 H), 3.91, (d, J = 2.0 Hz, 1 H), 4.14 (dd, J = 11.2, 5.2 Hz, 1 H), 4.32 (dd, J = 11.2, 3.2 Hz, 1 H), (m, 3 H), (m, 7 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 56.4, 60.2, 67.8, 114.7, 121.3, 125.7, 128.4, 128.5, 129.5, 136.5, 158.4; MS (E.I., 70 ev) m/z 226 (M + ). 2-(3-Phenyl-oxiranyl)-[1,3]dioxolane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 3.13 (dd, J = 3.8, 2.0 Hz, 1 H), 3.89 (d, J = 2.0 Hz, 1 H), (m, 2H), (m, 2 H), 5.00 (d, J = 3.8, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 55.2, 61.3, 65.3, 65.5, 102.3, 125.7, 128.3, 128.4, 136.2; GC-MS: m/z 192 (M + ). trans-2-chloromethyl-3-phenyl-oxirane: 1 H NMR (400.1 MHz, CDCl 3 ): δ 3.28 (ddd, J = 5.8, 4.8, 1.9 Hz, 1 H), 3.66 (dd, J = 11.8, 5.8 Hz, 1 H), 3.72 (dd, J = 11.8, 4.8, Hz, 1 H), 3.82 (d, J = 1.9 Hz, 1 H), (m, 5 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 44.3, 58.5, 60.9, 116.6, 125.6, 128.6, 135.9; GC-MS: m/z 168 (M + ). 2-(3-Phenyloxiranylmethyl)isoindole-1,3-dione: 1 H NMR (400.1 MHz, CDCl 3 ): δ 3.20 (ddd, J = 5.7, 4.7, 1.9 Hz, 1 H), 3.82 (dd, J = 14.3, 5.7 Hz, 1 H), 3.83 (d, J = 1.9 Hz, 1 H), 4.09 (dd, J = 14.3, 4.7 Hz, 1 H), (m, 5 H), 7.68 (dd, J = 5.5, 3.1 Hz, 2 H), ), 7.82 (dd, J = 5.5, 3.1 Hz, 2 H); 13 C NMR (100.6 MHz, CDCl 3 ): δ 39.3, 58.0, 58.9, 123.5, 125.6, 128.4, 128.5, 131.9, 134.2, 136.3, 168.0; MS (E.I., 70 ev): m/z 279 (M + ).

12 a-phenylcinnamonitrilepoxide: 1 H NMR (400.1 MHz, CD 2 Cl 2 ): δ 4.25 (1 H, s), (10 H, m); 13 C NMR (100.6 MHz, CD 2 Cl 2 ): δ 58.1, 69.0, 116.2, 125.4, 126.8, 128.9, 129.4, 130.1, 130.2, 132.4, MS (E.I., 70 ev): m/z = 222 (M+1 +, 8). 221 (M +, 42), 205 (35), 204 (45), 203 (24), 193 (30), 167 (41), 165 (39), 115 (100), 105 (61), 90 (31), 89 (40), 77 (39). (1) Nishiyama, H.; Shimada, T.; Itoh, H.; Sugiyama, H.; Motoyama, Y. Chem. Commun. 1997, (2) (a) Ziegler, M.; Monney, V.; Stoeckli-Evans, H.; Von Zelewsky, A.; Sasaki, I.; Dupic, G.; Daran, J. C.; Balavoine, G. G. A. Dalton Trans. 1999, ; (b) Kwong, H.-L.; Lee, W.-S. Tetrahedron: Asymmetry 2000, 11, (3) Greenwald, R.; Chaykovsky, E. J.; Corey, E. J. J. Org. Chem. 1962, 28, (4) Hartshorn, M. P.; Wallis, A. F. A. J. Chem. Soc. 1964,