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1 Supporting Information Iron Catalyst for xidation in Water: Surfactant-type Iron Complex-catalyzed Mild and Efficient xidation of Aryl Alkanes Using Aqueous TBHP as xidant in Water Takashi Nagano and Shū Kobayashi* Department of Chemistry, School of Science and Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo The HFRE Division, ERAT, Japan Science Technology Agency (JST) (Received July 4, 2008; CL ; Copyright The Chemical Society of Japan

2 Supporting Information Iron Catalyst for xidation in Water: Surfactant-Type Iron Complex-catalyzed Mild and Efficieant xidation of Aryl Alkanes Using Aqueous TBHP as xidant in Water Takashi Nagano and Shu _ Kobayashi Department of Chemistry, School of Science and Graduate School of Pharmaceutical Sciences, The University of Tokyo, The HFRE Division, ERAT, Japan Science and Technology Agency (JST), Hongo, Bunkyo-ku, Tokyo , Japan. Contents Experimental Section General and Starting Materials S-1 Syntheses of aryl alkanes 2d and 2g S-2 General procedure for benzylic oxidation S-2 Characterization data of the oxidation products S-3 References S-7 Copies of 1 H and 13 C NMR spectra of 2d, 2g, 3a-m, 5, 6, 8-10, 12 S-9 Experimental. General. 1 H and 13 C NMR spectra were recorded on a JEL JNM-ECX400 and JNM-ECX600 spectrometer. Tetramethylsilane (TMS) served as internal standard ( = 0 ppm) for 1 H NMR, and CDCl3 was used as internal standard ( = 77.0 ppm) for 13 C NMR. IR spectra were measured using a JASC FT/IR-610 spectrometer. High resolution ESI mass spectrometry was carried out using BRUKER DALTNICS BioTF II. Preparative thin-layer chromatography was carried out using Wakogel B-5F. Starting Materials. 1-Phenyloctane (2a), 4-pentylbiphenyl (2e), 4-nitroethylbenzene (2f), diphenylmethane (2l), fluorene (2m), indane (4), isochromane (7), triphenylmethane (11) and triphenylmethanol (13) were purchased from commercial sources. 1-(4-Methoxyphenyl)octane (2b), 1 1-(4-fluorophenyl)octane (2c), 1 S-1

3 1,1 -dimethylindane (2h), 2 1,1 -dimethyl-1,2,3,4-tetrahydronaphthalene (2i), 2 2,2-dimethylchromane (2j), 3 and N-phenylsulfonyl-1,2,3,4-tetrahydroquinoline (2k) 4 were prepared according to the literature procedures. Synthesis of 1-(4-t-butylphenyl)octane (2d). 5 This compound was prepared by similar method to those of 2b and 2c according to the literature. 1 t Bu MgBr + n-c 8 H 17 Br Fe(acac) 3 (3 mol %) Et 2, reflux, 30 min t Bu 2d 6 To a refluxing solution of 1-bromooctane (2.6 ml, 15 mmol) and Fe(acac) 3 (159 mg, 0.45 mmol) in Et 2 (100 ml) was added a solution of 4-t-butylmaganesium bromide, which was prepared from 1-bromo-4-t-butylbenezene (5.2 ml, 30 mmol) and Mg (802 mg, 33 mmol) in Et 2 (30 ml), in one portion. After 30 min, the reaction mixture was cooled to 0 C and quenched with 1N HCl. The organic layer was separated and the aqueous layer was extracted with Et 2. The combined organic layers were washed with brine, dried over MgS 4, filtered and evaporated. The residue was distilled under reduced pressure to give 2d (2.13 g, 58%). Boiling point: 93 C (0.15 mmhg). The NMR data are identical with those reported in the literature. 5 1 H NMR (500 MHz, CDCl 3 ): δ 7.29 (d, J = 7.9 Hz, 2H), 7.11 (d, J = 7.9 Hz, 2H), 2.56 (t, J = 7.9 Hz, 2H), 1.59 (m, 2H), (m, 19H), 0.88 (t, J = 6.8 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 148.2, 139.9, 128.0, 125.1, 35.5, 34.3, 31.9, 31.6, 31.4, 29.5 (overlap, 2C), 29.3, 22.7, IR (neat): 1517, 1463, 1363, 1269, 830, 570 cm 1. Synthesis of 4-trifluoromethanesulfonyloxyphenylethane (2g). To a solution of 4-ethylphenol (1.0 g, 8.19 mmol) and pyridine (1.1 ml, 13.9 mmol) Tf in CH 2 Cl 2 (15 ml) was added Tf 2 (1.8 ml, 10.6 mmol) at 0 C. After stirring at that temperature for 1 hour, an insoluble salt was removed by filtration using Celite and the filtrate was washed with 1N HCl and saturated NaHC 3. The organic layer was dried over MgS 4, filtered and evaporated. The residue was purified by flash column chromatography (Hexane/AcEt = 19/1) to give the desired compound as colorless oil (2.05 g, 98%). 1 H NMR (400 MHz, CDCl 3 ): δ 7.31 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 8.8 Hz, 2H), 2.73 (q, J = 7.6 Hz, 2H), 1.30 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ , 144.7, 129.5, 121.1, (q, J CF = Hz), 28.2, IR (neat): , 1423, 1251, 1216, 1142, 1018, 891, 839, 611, 496 cm 1. Anal. Calcd for C 9 H 9 3 F 3 S: C, 42.52; H, Found: C, 42.37; H, S-2

4 General procedure for iron-catalyzed benzylic oxidation: To a mixture of arylalkane (0.5 mmol) and Fe 2 (DS) 4 10H 2 6 (17 mg, mmol) in H 2 (0.5 ml) was added 70% aqueous TBHP solution (0.34 ml, 2.5 mmol) at 30 C. After stirring for 50 hours at that temperature, the reaction was quenched with a saturated aqueous NaHC 3 solution. The resulting mixture was extracted with Et 2 and the combined organic layers were dried over anhydrous MgS 4, filtered through a pad of Celite and concentrated in vacuo. The crude mixture was chromatographed on silica gel to give the desired ketone. 1-Phenyloctan-1-one (3a). 7 1 H NMR (400 MHz, CDCl 3 ): δ 7.96 (d, J = 7.6 Hz, 2H), 7.55 (t, J = 7.6 Hz, 1H), 7.45 (t, J = 7.6 Hz, 2H), 2.96 (t, J = 7.4 Hz, 2H), 1.73 (m, 2H), (m, 8H), 0.88 (t, J = 6.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 200.5, 137.0, 132.8, 128.5, 128.0, 38.6, 31.7, 29.3, 29.1, 24.3, 22.6, IR (neat): 2927, 1681, 1598, 1580, 1449, 1221, 751, 691, 570 cm 1. HRMS (ESI): calcd for C 14 H 21 + (M+H + ) , found (4-Methoxyphenyl)octan-1-one (3b). 8 1 H NMR (400 MHz, CDCl 3 ): δ 7.94 (d, J = Me 8.4 Hz, 2H), 6.93 (d, J = 8.4 Hz, 2H), 3.86 (s, 3H), 2.90 (t, J = 7.4 Hz, 2H), 1.72 (m, 2H), (m, 8H), 0.88 (t, J = 6.8 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 199.2, 163.2, 130.2, 130.1, 113.6, 55.4, 38.2, 31.7, 29.3, 29.1, 24.6, 22.6, IR (KBr): 2965, 2844, 1668, 1604, 1508, 1418, 1359, 1279, 1258, 1176, 1021, 956, 834, 591, 578 cm 1. 1-(4-Fuluorophenyl)octan-1-one (3c). 8 1 H NMR (400 MHz, CDCl 3 ): δ (m, F 2H), (m, 2H), 2.93 (t, J = 7.4 Hz, 2H), 1.73 (m, 2H), (m, 10H), 0.88 (t, J = 6.6 Hz). 13 C NMR (100 MHz, CDCl 3 ): δ 198.9, (d, J CF = Hz), (d, J CF = 2.9 Hz), (d, J CF = 8.6 Hz), (d, J CF = 22.1 Hz), 38.5, 31.7, 29.3, 29.1, 24.3, 22.6, IR (KBr): 2919, 2849, 1681, 1600, 1508, 1244, 849, 822, 772, 600, 567 cm 1. HRMS (ESI): calcd for C 14 H 20 F + (M+H + ) , S-3

5 found (4-t-Butylphenyl)octan-1-one (3d). 1 H NMR (400 MHz, CDCl 3 ): δ 7.90 (d, J = 8.0, t Bu 2H), 7.47 (d, J = 8.0 Hz, 2H), 2.94 (t, J = 7.4 Hz, 2H), 1.72 (m, 2H), (m, 19H), 0.88 (t, J = 7.0, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 200.3, 156.5, 134.5, 128.0, 125.4, 38.5, 35.0, 31.7, 31.1, 29.3, 29.1, 24.5, 22.6, IR (neat): 2959, 1683, 1606, 1465, 1407, 1363, 1269, 1226, 1107, 734, 582 cm 1. HRMS (ESI): calcd for C 18 H 29 + (M+H + ) , found (1,1'-Biphenyl)-4-yl-1-pentanone (3e). 9 1 H NMR (400 MHz, CDCl 3 ): δ 8.03 (d, J = Ph 8.0 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 6.8 Hz, 2H), (m, 3H), 2.99 (t, J = 7.2 Hz, 2H), 1.75 (m, 2H), 1.43 (m, 2H), 0.97 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 200.2, 145.5, 139.9, 135.7, 128.9, 128.6, 128.1, 127.2, 127.1, 38.3, 26.5, 22.5, IR (KBr): 2952, 2868, 1675, 1602, 1449, 1404, 1375, 1344, 1270, 1212, 980, 850, 742, 692, 575 cm 1. HRMS (ESI): calcd for C 17 H 18 Na + (M+Na + ) , found Nitroacetophenone (3f) H NMR (400 MHz, CDCl 3 ): δ 8.34 (d, J = 8.8 Hz, 2H), 2 N 8.13 (d, J = 8.8 Hz, 2H), 2.70 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 196.3, 150.2, 141.3, 129.3, 123.8, IR (KBr): 3109, 1694, 1608, 1520, 1349, 1263, 963, ,691, 504 cm 1. HRMS (ESI): calcd for C 8 H 8 N 3 + (M+H + ) , found (Trifluoromethanelsulfonyloxy)acetophenone (3g) H NMR (400 MHz, CDCl 3 ): Tf δ 8.07 (d, J = 8.8 Hz, 2H), 7.39 (d, J = 8.8 Hz, 2H), 2.64 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 196.1, 152.4, 136.8, 130.6, 121.6, (q, J CF = Hz), IR (neat): 1693, 1595, 1497, 1427, 1214, 1139, 891, 611, 526 cm 1. HRMS (ESI): calcd for C 9 H 8 F (M+H + ) , found S-4

6 3,3-Dimethyl-1-indanone (3h) H NMR (400 MHz, CDCl 3 ): δ 7.70 (d, J = H), 7.62 (m, 1H), 7.50 (d, J = 7.6, 1H), 7.37 (m, 1H), 2.60 (s, 2H), 1.42 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): δ 206.0, 163.8, 135.2, 134.9, 127.3, 123.5, 123.2, 52.8, 38.4, IR (neat): 2961, 1716, 1604, 1472, 1324, 1291, 1247, 1092, 1037, 1016, 913, 734, 530 cm 1. HRMS (ESI): calcd for C 11 H 13 + (M+H + ) , found ,4-Dimethyl-1-tetralone (3i) H NMR (400 MHz, CDCl 3 ): δ 8.02 (dd, J = 8.0, 1.2, 1H), 7.53 (dt, J = 8.0, 1.6, 1H), 7.42 (dd, J = 7.6, 0.8, 1H), 7.29 (dt, J = 7.8, 1.2, 1H), 2.73 (t, J = 7.0 Hz, 2H), 2.03 (t, J = 7.0 Hz, 2H), 1.40 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): δ 198.4, 152.2, 133.8, 131.0, 127.2, 126.2, 125.8, 37.0, 35.0, 33.8, IR (neat): 2964, 1685, 1600, 1284, 1249, 1198, 913, 768, 733, 569 cm 1. HRMS (ESI): calcd for C 12 H 15 + (M+H + ) , found ,3-Dihydro-2,2 -dimethylchromen-4-one (3j) H NMR (400 MHz, CDCl 3 ): δ 7.86 (dd, J = 7.6, 1.8 Hz, 1H), 7.47 (m, 1H), 6.98 (t, J = 7.6 Hz, 1H), 6.93 (d, J = 8.4 Hz, 1H), 2.73 (s, 2H), 1.47 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): δ 192.4, 159.8, 136.0, 126.4, 120.5, 120.0, 118.2, 79.0, 48.7, IR (KBr): 2978, 2934, 1686, 1605, 1456, 1306, 1256, 1119, 1024, 929, 896, 766, 571 cm 1. HRMS (ESI): calcd for C 11 H (M+H + ) , found Phenylsurfonyl-1,2,3,4-tetrahydroquinolin-4-one (3k). 1 H NMR (400 MHz, CDCl 3 ): δ 7.95 (dd, J = 8.0, 1.6 Hz, 1H), 7.87 (d, J = 9.2 Hz, 1H), (m, 4H), 7.45 (t, J = 8.0 Hz, 2H), 7.29 (t, J = 8.0 Hz, 2H), 4.25 (t, J = 6.4 Hz, 2H), 2.38 (t, J = 6.4 Hz, 2H). 13 C NMR (100 MHz, CDCl 3 ): δ 192.5, 142.1, 139.6, 134.7, 133.5, 129.5, 127.7, 126.7, 125.7, 124.5, 46.2, IR (KBr): 1681, 1598, 1454, 1364, 1351, 1168, 760, 736, 590 cm 1. HRMS (ESI): calcd for C 15 H 15 N 3 + (M+H + ) , found N S 2 Ph S-5

7 Benzophenone (3l) H NMR (400 MHz, CDCl 3 ): δ 7.81 (d, J = 7.6 Hz, 4H), 7.60 (t, J = 7.6 Hz, 2H), 7.49 (t, J = 7.6 Hz, 4H). 13 C NMR (100 MHz, CDCl 3 ): δ 196.6, 137.4, 132.3, 129.9, IR (neat): 1656, 1599, 1577, 1447, 1317, 1278, 941, 920, 764, 700, 638 cm 1. HRMS (ESI): calcd for C 13 H 10 Na + (M+Na + ) , found Fluorenone (3m) H NMR (400 MHz, CDCl 3 ): δ 7.65 (brd, J = 7.2 Hz, 2H), (m, 4H), 7.29 (dt, J = 7.2, 1.6 Hz, 2H). 13 C NMR (100 MHz, CDCl 3 ): δ 193.8, 144.3, 134.6, 134.0, 128.9, 124.1, IR (KBr): 1714, 1611, 1599, 1450, 1298, 918, 736 cm 1. HRMS (ESI): calcd for C 13 H 9 + (M+H + ) , found Indanone (5) H NMR (400 MHz, CDCl 3 ): δ 7.76 (d, J = 7.6 Hz, 1H), 7.59 (m, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.37 (m, 1H), 3.15 (t, J = 5.8 Hz, 2H), 2.70 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ): δ 207.1, 155.1, 137.0, 134.6, 127.2, 126.7, 123.7, 36.2, (t-Butylperoxy)indan-3-one (6) H NMR (400 MHz, CDCl 3 ): δ (m, 2H), t Bu 7.66 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 5.65 (dd, J = 6.4, 2.0 Hz, 1H), 2.99 (dd, J = 19.2, 6.4 Hz, 1H), 2.83 (dd, J = 19.2, 2.4 Hz, 1H), 1.27 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ): δ 203.1, 151.0, 137.4, 134.7, 129.9, 127.5, 123.3, 80.7, 79.0, 42.7, ,4-Dihydroisochromen-1-one (8) H NMR (400 MHz, CDCl 3 ): δ 8.11 (d, J = 8.0 Hz, 1H), 7.55 (m, 1H), 7.41 (t, J = 7.6 Hz, 1H), 7.28 (d, J = 7.4 Hz), 4.55 (t, J = 6.0 Hz, 2H), 3.07 (t, J = 6.0 Hz, 2H). 13 C NMR (100 MHz, CDCl 3 ): δ 165.1, 139.5, 133.6, 130.2, 127.5, 127.2, 125.1, 67.2, (tert-Butylperoxy)-1H-isochromen-4(3H)-one (9). 1 H NMR (400 MHz, CDCl 3 ): δ t Bu 8.03 (d, J = 8.0 Hz, 1H), 7.66 (dt, J = 1.4, 8.0 Hz, 1H), 7.56 (dt, J = 1.4, 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 6.21 (s, 1H), 4.86 (d, J = S-6

8 17.2, 1H), 4.38 (d, J = 17.2 Hz, 1H), 1.33 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ): δ 193.5, 135.9, 134.4, 130.1, 129.5, 127.1, 126.0, 99.4, 81.6, 66.2, IR (neat): 2969, 1703, 1604, 1294, 1103, 1011, 769, 543 cm 1 +. HRMS (ESI): calcd for C 13 H 16 Na 4 (M+Na + ) , found (tert-Butylperoxy)-3,4-dihydro-1H-isochromene (10) H NMR (400 MHz, t Bu 1.36 (s, 9H). CDCl 3 ): δ 7.35 (d, J = 7.2 Hz, 1H), (m, 2H), 7.15 (d, J = 7.6 Hz, 1H), 6.05 (s, 1H), 4.22 (dt, J = 12.4, 3.2 Hz, 1H), 4.01 (ddd, J = 11.2, 5.8, 1.4 Hz, 1H), 3.04 (m, 1H), 2.61 (dd, J = 16.4, 2.8 Hz, 1H), 13 C NMR (100 MHz, CDCl 3 ): δ 135.6, 130.2, 128.8, 128.7, 128.3, 126.2, 99.2, 81.0, 58.1, 27.8, IR (neat): 2973, 1363, 1198, 1095 (C--), 1002, 746 cm 1. 1-(t-Butylperoxy)-1,1,1-triphenylmethane (12). 18,21 1 H NMR (400 MHz, CDCl 3 ): δ Ph Ph t Bu Ph (m, 6H), (m, 9H), 0.99 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ): δ 143.6, 129.2, 127.3, 127.0, 90.6, 79.7, IR (KBr): 2980, 1596, 1491, 1450, 1362, 1184, 1002, 908, 871, 705 cm 1. Anal. Calcd for C 23 H 24 2 : C, 83.10; H, Found: C, 83.08; H, References (1) Nagano, T.; Hayashi, T. rg. Lett. 2004, 6, (2) Reetz, M. T.; Westermann, J.; Kyung, S.-H. Chem. Ber. 1985, 118, (3) Bernier, D.; Brückner, R. Synthesis 2007, (4) Uchiyama, M.; Matsumoto, Y.; Nakamura, S.; hwada, T.; Kobayashi, N.; Yamashita, N.; Matsumiya, A.; Sakamoto, T. J. Am. Chem. Soc. 2004, 126, (5) Yamada, Y. M. A.; Takeda, K.; Takahashi, H.; Ikegami, S. J. rg. Chem. 2003, 68, (6) Tolbert, S. H.; Sieger, P.; Stucky, G. D.; Aubin, S. M. J.; Wu, C.-C.; Hendrickson, D. N. J. Am. Chem. Soc. 1997, 119, (7) Ackermann, L.; Kaspar, L. T. J. rg. Chem. 2007, 72, (8) Muzart, J.; N Ait Ajjou, A. Synthesis 1993, 785. (9) Picard, F.; Schulz, T.; Hartmann, R. W. Bioorg. Med. Chem. 2002, 10, 437. (10) Fujita, K.; Tanino, N.; Yamaguchi, R. rg. Lett. 2007, 9, 109. S-7

9 (11) Chung, C. W. Y.; Toy, P. H. Tetrahedron 2005, 61, 709. (12) Chassaing, S.; Kumarraja, M.; Pale, P.; Sommer, J. rg. Lett. 2007, 9, (13) Chen, F.; Yang, J.; Zhang, H.; Guan, C.; Wan, J. Synth Commun. 1995, 25, (14) Deagostino, A.; Farina, V.; Prandi, C.; Zavattaro, C.; Venturello, P. Eur. J. rg. Chem. 2006, (15) Xing, D.; Guan, B.; Cai, G.; Fang, Z.; Yang, L.; Shi, Z. rg. Lett. 2006, 8, 693. (16) Barluenga, J.; Trincado, M.; Rubio, E.; González, J. M. Angew. Chem., Int. Ed. 2006, 45, (17) dedra, A.; Datta, S.; Liu, R.-S. J. rg. Chem. 2007, 72, (18) Muzart, J.; N Ait Ajjou, A. J. Mol. Catal. 1994, 92, 141. (19) Silvestre, S. M.; Salvador, A. R. Tetrahedron 2007, 63, (20) Catino, A. J.; Nichols, J. M.; Choi, H.; Gottipamula, S.; Doyle, M. P. rg. Lett. 2005, 7, (21) Barton, D. H. R.; Le Gloahec, V. N. Tetrahedron 1998, 54, S-8

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