Supporting Information for Fe-Catalyzed Reductive Coupling of Unactivated Alkenes with. β-nitroalkenes. Contents. 1. General Information S2

Supporting Information for Fe-Catalyzed Reductive Coupling of Unactivated Alkenes with β-nitroalkenes Jing Zheng, Dahai Wang, and Sunliang Cui* College of Pharmaceutical Sciences, Zhejiang University, Hangzhou, Zhejiang 310058, China E-mail: slcui@zju.edu.cn Contents 1. General Information S2 2. Typical Synthesis Procedure of 3a S2-S3 3. Characterization of 3 and 6 S3-S27 4. Radical Scavenger Test S27-S28 5. Copies of NMR Spectra S29-S80 S1

1. General Information: Infrared spectra were obtained on a FTIR spectrometer. 1 H NMR and 13 C NMR spectra were recorded on BRUKER AVANCE III 500 or BRUKER AVANCE III 400 spectrometer. CDCl 3 were used as solvent. Chemical shifts were referenced relative to residual solvent. The following abbreviations are used to describe peak patterns where appropriate: br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dq = double quartet. Coupling constants (J) are reported in Hertz (Hz). HRMS were performed on Waters GCT Premier Time of Flight Mass Spectrometer (EI). Melting points were measured with micro melting point apparatus. Fe(acac) 3, PhSiH 3, EtOH were commercial available, and nitroalkenes were prepared from aldehydes and nitromethane. The following alkenes were commercially available: 2-methyl-2-propen-1-ol (2c, and precursor of 2a), 3-Chloro-2-methylpropene (precursor of 2b), 3-methyl-3-buten-1-ol (2d), N-(tert-Butoxycarbonyl)-4-piperidone (precursor of 2e), 3,3-dimethylallylbromide (precursor of 2f), but-3-enenitrile (2g), 4-allylanisole (2h), allyltrimethylsilane (2i), cyclohexene (2j), 1-methyl-1-cyclohexene (2k), bicyclo[2.2.1]hept-2-ene (2l), (S)-(-)-β-Citronellol (2m), L-Menthol (precursor to 2n). 2. Typical Procedure for Synthesis of 3a: S2

1a NO 2 + OBn 2a (10 mol %) Fe(acac) 3 PhSiH 3 (2 equiv) EtOH, 60 o C 3a OBn A Schlenk tube containing β-nitrostyrene 1a (30 mg, 0.2 mmol), Fe(acac) 3 (7.2 mg, 10 mol %) were evacuated and purged with Argon three times. Afterwards, (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), PhSiH 3 (43.2 mg, 0.4 mmol) and 2 ml EtOH was added via syringe. The solution was kept at 60 o C for 8 h. Then the solution was diluted with CH 2 Cl 2 and transferred to a round bottom flask. Silica gel was added to the flask and volatiles were evaporated under vacuum. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent to give 3a as a pale yellow liquid (48mg, 90% yield). 3. Characterization of 3 and 6: (E)-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)benzene (3a) Prepared following the Typical Procedure in 90% yield as a pale yellow liquid (48 mg, 0.180 mmol) for 3a, from β-nitrostyrene 1a (30 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. S3

Ph OBn 3a Pale yellow liquid; R f = 0.46 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 400MHz), δ: 7.38-7.34 (m, 6H), 7.32-7.28 (m, 3H), 7.22-7.28 (m, 1H), 6.38 (d, J = 16.4 Hz, 1H), 6.29 (d, J = 16.4 Hz, 1H), 4.55 (s, 2H), 3.29 (s, 2H), 1.16 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 138.9, 138.1, 138.0, 128.6, 128.4, 127.6, 127.5, 127.0, 126.9, 126.3, 79.5, 73.4, 38.0, 24.8; IR (film) v: 3060, 3028, 2960, 2925, 2855, 1692, 1647, 1547, 1202, 1098, 1024, 739, 694 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 22 O (M + ): 266.1671; Found: 266.1672. (E)-(3,3-dimethyl-4-phenoxybut-1-en-1-yl)benzene (3b) Prepared following the Typical Procedure in 84% yield as a pale yellow liquid (42 mg, 0.167 mmol) for 3b, from β-nitrostyrene 1a (30 mg, 0.2 mmol), ((2-methylallyl)oxy)benzene 2b (59.2 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using petroleum ether as eluent. Ph OPh 3b Pale yellow liquid; R f = 0.52 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 400MHz), δ: 7.41-7.39 (m, 2H), 7.34-7.27 (m, 4H), 7.24-7.20 (m, S4

1H), 6.97-6.93 (m, 3H), 6.47 (d, J = 16.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 3.78 (s, 2H), 1.28 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 159.5, 137.8, 137.2, 129.5, 128.6, 127.5, 127.2, 126.3, 120.7, 114.8, 76.6, 37.7, 24.7; IR (film) v: 3065, 3031, 2959, 2924, 2858, 1595, 1530, 1496, 1296, 1077, 1043, 920, 881, 825 cm -1 ; HRMS (EI) (m/z): calcd for C 18 H 20 O (M + ): 252.1514; Found: 252.1512. (E)-2,2-dimethyl-4-phenylbut-3-en-1-ol (3c) Prepared following the Typical Procedure in 70% yield as a yellow liquid (24.6 mg, 0.140 mmol) for 3c, from β-nitrostyrene 1a (30 mg, 0.2 mmol), 2-methyl-2-propen-1-ol 2c (28.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:10) as eluent. Yellow liquid; R f = 0.15 (EtOAc/Petroleum ether 1:10); 1 H NMR (CDCl 3, 400MHz), δ: 7.40-7.37 (m, 2H), 7.33-7.29 (m, 2H), 7.24-7.20 (m, 1H), 6.42 (d, J = 16.4 Hz, 1H), 6.18 (d, J = 16.4 Hz, 1H), 3.43 (s, 2H), 1.14 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 137.4, 136.9, 128.8, 128.7, 127.4, 126.3, 71.8, 39.0, 24.0; IR (film) v: 3456, 3065, 2963, 2860, 1547, 1460, 1390, 1370, 1266, 1135, 1074, 971, 740, 701, 604 cm -1 ; HRMS (EI) (m/z): S5

calcd for C 12 H 16 O (M + ): 176.1201; Found: 176.1201. (E)-3,3-dimethyl-5-phenylpent-4-en-1-ol (3d) Prepared following the Typical Procedure in 67% yield as a yellow liquid (24 mg, 0.126 mmol) for 3d, from β-nitrostyrene 1a (30 mg, 0.2 mmol), 3-methyl-3-buten-1-ol 2d (33.6 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:10) as eluent. Yellow liquid; R f = 0.15 (EtOAc/Petroleum ether 1:10); 1 H NMR (CDCl 3, 400MHz), δ: 7.37-7.35 (m, 2H), 7.32-7.28 (m, 2H), 7.23-7.19 (m, 1H), 6.32 (d, J = 16.4 Hz, 1H), 6.23 (d, J = 16.4 Hz, 1H), 3.69 (t, J = 7.2 Hz, 2H), 1.72 (t, J = 7.2 Hz, 2H), 1.15 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 140.1, 137.7, 128.7, 127.2, 126.23, 126.20, 60.3, 45.7, 35.6, 27.7; IR (film) v: 3540, 3026, 2957, 2925, 2857, 1726, 1692, 1647, 1528, 1532, 1462, 1391, 1371, 1132, 972, 788 cm -1 ; HRMS (EI) (m/z): calcd for C 13 H 18 O (M + ): 190.1358; Found: 190.1356. tert-butyl (E)-4-methyl-4-styrylpiperidine-1-carboxylate (3e) Prepared following the Typical Procedure in 42% yield as a yellow S6

liquid (25 mg, 0.083 mmol) for 3e, from β-nitrostyrene 1a (30 mg, 0.2 mmol), tert-butyl 4-methylenepiperidine-1-carboxylate 2e (78.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:20) as eluent. Ph N Boc 3e Pale yellow liquid; R f = 0.25 (EtOAc/Petroleum ether 1:20); 1 H NMR (CDCl 3, 400MHz), δ: 7.37-7.35 (m, 2H), 7.33-7.29 (m, 2H), 7.23-7.19 (m, 1H), 6.35 (d, J = 16.4 Hz, 1H), 6.17 (d, J = 16.4 Hz, 1H), 3.53-3.51 (m, 2H), 3.40-3.33 (m, 2H), 1.71-1.67 (m, 4H), 1.46 (s, 9H), 1.13(s, 3H); 13 C NMR (CDCl 3, 100MHz), δ: 155.1, 138.7, 137.7, 128.7, 127.4, 127.3, 126.1, 79.4, 37.0, 34.9, 29.8, 28.6, 27.0; IR (film) v: 2965, 2856, 2361, 1947, 1720, 1601, 1365, 1251, 1108, 1023, 969, 911 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 27 NO 2 (M + ): 301.2042; Found: 301.2040. (E)-(3,3-dimethyl-5-phenoxypent-1-en-1-yl)benzene (3f) Prepared following the Typical Procedure in 62% yield as a yellow liquid (33 mg, 0.124 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), ((3-methylbut-2-en-1-yl)oxy)benzene 2f (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at S7

60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. Ph OPh 3f Pale yellow liquid; R f = 0.45 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 500MHz), δ: 7.38-7.37 (m, 2H), 7.32-7.29 (m, 2H), 7.27-7.24 (m, 2H), 7.22-7.20 (m, 1H), 6.92 (t, 1H), 6.88-6.86 (m, 2H), 6.35 (d, J = 16.0 Hz, 1H), 6.25 (d, J = 16.0 Hz, 1H), 4.00 (t, J = 7.0 Hz, 2H), 1.94 (t, J = 7.0 Hz, 2H), 1.21 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 159.0, 139.7, 137.8, 129.5, 128.7, 127.1, 126.5, 126.2, 120.6, 114.6, 65.2, 41.8, 35.6, 27.8; IR (film) v: 3063, 3029, 2958, 2929, 2870, 1595, 1532, 1496, 1296, 1078, 1031, 783, 749, 691, 644 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 22 O (M + ): 266.1671; Found: 266.1669. (E)-3-methyl-5-phenylpent-4-enenitrile (3g) Prepared following the Typical Procedure in 56% yield as a pale yellow liquid (19 mg, 0.111 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), but-3-enenitrile 2g (26.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using petroleum ether as eluent. S8

Pale yellow liquid; R f = 0.36 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 500MHz), δ: 7.37-7.36 (m, 2H), 7.33-7.30 (m, 2H), 7.26-7.23 (m, 1H), 6.49 (d, J = 16.0 Hz, 1H), 6.13 (dd, J 1 = 15.5 Hz, J 2 = 7.5 Hz, 1H), 2.79-2.73 (m, 1H), 2.50-2.41 (m, 2H), 1.29 (d, J = 7.0 Hz, 3H); 13 C NMR (CDCl 3, 100MHz), δ: 136.7, 131.6, 130.8, 128.7, 127.8, 126.5, 118.6, 34.2, 25.1, 19.9; IR (film) v: 3060, 3027, 2964, 2924, 2856, 1692, 1547, 1458, 1461, 1390, 1371, 1073, 791, 739 cm -1 ; HRMS (EI) (m/z): calcd for C 12 H 13 N (M + ): 171.1048; Found: 171.1048. (E)-1-methoxy-4-(2-methyl-4-phenylbut-3-en-1-yl)benzene (3h) Prepared following the Typical Procedure in 72% yield as a pale yellow liquid (36 mg, 0.143 mmol) for 3h, from β-nitrostyrene 1a (30 mg, 0.2 mmol), 1-allyl-4-methoxybenzene 2h (59.2 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:50) as eluent. Pale yellow liquid; R f = 0.32 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 400MHz), δ: 7.35-7.27 (m, 4H), 7.22-7.18 (m, 1H), 7.10 (d, J = S9

8.4 Hz, 2H), 6.83 (d, J = 8.4 Hz, 2H), 6.32 (d, J = 16.0 Hz, 1H), 6.19 (dd, J 1 = 16.0 Hz, J 2 = 6.8 Hz, 1H), 3.80 (s, 3H), 2.74-2.70 (m, 1H), 2.60-2.54 (m, 2H), 1.09 (d, J = 6.4 Hz, 3H); 13 C NMR (CDCl 3, 100MHz), δ: 157.9, 138.0, 136.2, 132.7, 130.3, 128.6, 128.3, 127.0, 126.1, 113.7, 55.4, 42.8, 39.1, 19.9; IR (film) v: 3027, 2959, 2923, 2845, 1611, 1549, 1511, 1299, 1246, 1178, 1076, 907, 833, 747 cm -1 ; HRMS (EI) (m/z): calcd for C 18 H 20 O (M + ): 252.1514; Found: 252.1575. (E)-trimethyl(2-methyl-4-phenylbut-3-en-1-yl)silane (3i) Prepared following the Typical Procedure in 45% yield as a pale yellow liquid (19.6 mg, 0.090 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), allyltrimethylsilane 2i (45.6 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. Ph 3i TMS Pale yellow liquid; R f = 0.42 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 400MHz), δ: 7.35-7.33 (m, 2H), 7.31-7.27 (m, 2H), 7.21-7.17 (m, 1H), 6.32 (d, J = 16.0 Hz, 1H), 6.12 (dd, J 1 = 16.0 Hz, J 2 = 8.0 Hz, 1H), 2.55-2.45 (m, 1H), 1.12 (d, J = 6.8 Hz, 3H), 0.79-0.69 (m, 2H), 0.02 (s, 9H); 13 C NMR (CDCl 3, 100MHz), δ: 139.2, 138.1, 128.6, 126.8, 126.7, S10

126.1, 34.1, 25.6, 24.6, 0.47; IR (film) v: 2925, 2856, 1641, 1498, 1458, 1374, 1254, 1174, 845, 748, 699 cm -1 ; HRMS (EI) (m/z): calcd for C 14 H 22 Si (M + ): 218.1491; Found: 218.1490. (E)-(2-cyclohexylvinyl)benzene (3j) Prepared following the Typical Procedure in 42% yield as a white liquid (15.6 mg, 0.084 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), cyclohexene 2j (32.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using petroleum ether as eluent. Ph 3j White liquid; R f = 0.7 (Petroleum ether); 1 H NMR (CDCl 3, 500MHz), δ: 7.35-7.34 (m, 2H), 7.30-7.27 (m, 2H), 7.20-7.16 (m, 1H), 6.34 (d, J = 16.5 Hz, 1H), 6.18 (dd, J 1 = 16.0 Hz, J 2 = 7.0 Hz, 1H), 2.16-2.10 (m, 1H), 1.82-1.75 (m, 4H), 1.70-1.66 (m, 1H), 1.34-1.30 (m, 2H), 1.21-1.17 (m, 2H), 0.90-0.87 (m, 1H); 13 C NMR (CDCl 3, 100MHz), δ: 138.2, 137.0, 128.6, 127.3, 126.9, 126.1, 41.3, 33.1, 26.3, 26.2; IR (film) v: 3066, 3032, 2924, 2853, 1623, 1607, 1547, 1532, 1179, 1108, 1027, 921, 873, 751 cm -1 ; HRMS (EI) (m/z): calcd for C 14 H 18 (M + ): 186.1409; Found: 186.1402. (E)-(2-(1-methylcyclohexyl)vinyl)benzene (3k) Prepared following S11

the Typical Procedure in 45% yield as a white liquid (18 mg, 0.090 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), 1-methylcyclohex-1-ene 2k (38.4 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using petroleum ether as eluent. Ph 3k White liquid; R f = 0.72 (Petroleum ether); 1 H NMR (CDCl 3, 400MHz), δ: 7.39-7.36 (m, 2H), 7.32-7.28 (m, 2H), 7.21-7.17 (m, 1H), 6.32 (d, J = 16.4 Hz, 1H), 6.21 (d, J = 16.4 Hz, 1H), 1.63-1.58 (m, 2H), 1.53-1.49 (m, 3H), 1.44-1.36 (m, 4H), 1.07 (s, 3H), 0.90-0.87 (m, 1H); 13 C NMR (CDCl 3, 100MHz), δ: 141.2, 138.4, 128.6, 126.8, 126.08, 126.06, 38.1, 36.3, 29.9, 26.5, 22.6; IR (film) v: 3061, 3026, 2925, 2854, 1495, 1433, 1073, 1025, 744, 692, 602 cm -1 ; HRMS (EI) (m/z): calcd for C 15 H 20 (M + ): 200.1565; Found: 200.1568. 2-((E)-styryl)bicyclo[2.2.1]heptane (3l) Prepared following the Typical Procedure in 50% yield as a white liquid (20 mg, 0.101 mmol) for 3f, from β-nitrostyrene 1a (30 mg, 0.2 mmol), bicyclo[2.2.1]hept-2-ene 2l (37.6 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The S12

purification was performed by flash column chromatography on silica gel using petroleum ether as eluent. White liquid; R f = 0.42 (Petroleum ether); 1 H NMR (CDCl 3, 500MHz), δ: 7.35-7.33 (m, 2H), 7.30-7.27 (m, 2H), 7.20-7.16 (m, 1H), 6.30 (d, J = 16.0 Hz, 1H), 6.13 (dd, J 1 = 16.0 Hz, J 2 = 8.0 Hz, 1H), 2.29-2.26 (m, 2H), 2.15 (d, 1H), 1.59-1.57 (m, 1H), 1.55-1.51 (m, 1H), 1.47-1.44 (m, 1H), 1.41-1.36 (m, 1H), 1.31-1.28 (m, 1H), 1.23-1.21 (m, 1H), 1.18-1.15 (m, 1H), 0.89-0.88 (m, 1H); 13 C NMR (CDCl 3, 100MHz), δ: 138.1, 136.6, 128.6, 127.4, 126.8, 126.1, 45.6, 42.8, 38.1, 36.8, 36.0, 29.9, 29.2; IR (film) v: 3060, 3027, 2951, 2867, 1605, 1498, 1452, 965, 746, 697 cm -1 ; HRMS (EI) (m/z): calcd for C 15 H 18 (M + ): 198.1409; Found: 198.1401. (E)-1-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-4-methylbenzene (6a) Prepared following the Typical Procedure in 80% yield as a pale yellow liquid (45 mg, 0.161 mmol) for 6a, from (E)-1-methyl-4-(2-nitrovinyl)benzene 1b (33 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. S13

OBn Me 6a Pale yellow liquid; R f = 0.39 (EtOAc/Petroleum ether 1:100) 1 H NMR (CDCl 3, 400MHz), δ: 7.27-7.26 (m, 4H), 7.20-7.17 (m, 3H), 7.03 (d, J = 7.6 Hz, 2H), 6.27 (d, J = 16.4 Hz, 1H), 6.16 (d, J = 16.4 Hz, 1H), 4.47 (s, 2H), 3.21 (s, 2H), 2.25 (s, 3H), 1.08 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 139.0, 137.1, 136.7, 135.2, 129.3, 128.4, 127.53, 127.49, 126.7, 126.1, 79.5, 73.4, 37.9, 24.8, 21.3; IR (film) v: 3028, 2961, 2926, 2861, 1692, 1645, 1548, 1459, 1101, 1025, 969, 800, 737, 698 cm -1 ; HRMS (EI) (m/z): calcd for C 20 H 24 O (M + ): 280.1827; Found: 280.1826. (E)-1-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-4-methoxybenzene (6b) Prepared following the Typical Procedure as a pale yellow liquid (31mg, 53% yield). Prepared following the Typical Procedure in 53% yield as a pale yellow liquid (31 mg, 0.105 mmol) for 6b, from (E)-1-methoxy-4-(2-nitrovinyl)benzene 1c (36 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:50) as eluent. S14

Pale yellow liquid; R f = 0.34 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 500MHz), δ: 7.36-7.34 (m, 4H), 7.31-7.28 (m, 3H), 6.84 (d, J = 8.5 Hz, 2H), 6.32 (d, J = 16.0 Hz, 1H), 6.15 (d, J = 16.0 Hz, 1H), 4.55 (s, 2H), 3.81 (s, 3H), 3.28 (s, 2H), 1.15 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 158.8, 139.0, 136.0, 130.8, 128.4, 127.6, 127.5, 127.3, 126.2, 114.0, 79.6, 73.4, 55.4, 37.9, 24.8; IR (film) v: 3030, 2959, 2861, 1547, 1510, 1364, 1290, 1247, 1180, 1098, 1033, 909, 853, 812 cm -1 ; HRMS (EI) (m/z): calcd for C 20 H 24 O 2 (M + ): 296.1776; Found: 296.1775. (E)-4-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-N,N-dimethylanili ne (6c) Prepared following the Typical Procedure in 50% yield as a pale yellow liquid (31 mg, 0.100 mmol) for 6c, from (E)-N,N-dimethyl-4-(2-nitrovinyl)aniline 1d (38 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:20) as eluent. S15

Pale yellow liquid; R f = 0.38 (EtOAc/Petroleum ether 1:20); 1 H NMR (CDCl 3, 400MHz), δ: 7.34-7.32 (m, 4H), 7.27-7.24 (m, 3H), 6.67 (d, J = 8.8 Hz, 2H), 6.28 (d, J = 16.4 Hz, 1H), 6.07 (d, J = 16.4 Hz, 1H), 4.54 (s, 2H), 3.26 (s, 2H), 2.93 (s, 6H), 1.13 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 149.9, 139.1, 134.0, 128.4, 127.5, 127.4, 127.1, 126.8, 126.6, 112.8, 79.8, 73.4, 40.8, 37.8, 24.9; IR (film) v: 3028, 2962, 2927, 2858, 1610, 1521, 1452, 1354, 1164, 1103, 847, 806, 738 cm -1 ; HRMS (EI) (m/z): calcd for C 21 H 27 NO (M + ): 309.2093; Found: 309.2093. (E)-1-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-4-fluorobenzene (6d) Prepared following the Typical Procedure in 87% yield as a pale yellow liquid (49 mg, 0.172 mmol) for 6d, from (E)-1-fluoro-4-(2-nitrovinyl)benzene 1e (34 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. S16

OBn F 6d Pale yellow liquid; R f = 0.32 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 400MHz), δ: 7.30-7.18 (m, 7H), 6.93-6.89 (m, 2H), 6.26 (d, J = 16.4 Hz, 1H), 6.12 (d, J = 16.4 Hz, 1H), 4.47 (s, 2H), 3.21 (s, 2H), 1.07 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ:162.1 (d, J = 244.0 Hz), 138.9, 137.88 (d, J = 2.0 Hz), 134.15 (d, J = 3.0 Hz), 128.24 (d, J = 62.0 Hz), 127.7, 127.61, 127.56, 125.8, 115.41 (d, J = 21.0 Hz), 79.4, 73.4, 37.9, 24.8; IR (film) v: 3035, 2963, 2928, 2859, 1644, 1566, 1548, 1510, 1227, 1099, 968, 812, 736, 697 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 21 FO (M + ): 284.1576; Found: 284.1573. (E)-1-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-4-bromobenzene (6e) Prepared following the Typical Procedure in 58% yield as a pale yellow liquid (40 mg, 0.116 mmol) for 6e, from (E)-1-bromo-4-(2-nitrovinyl)benzene 1f (45 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:50) as eluent. S17

Pale yellow liquid; R f = 0.28 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 500MHz), δ: 7.41 (d, J = 8.5 Hz, 2H), 7.34-7.33 (m, 4H), 7.30-7.27 (m, 1H), 7.22 (d, J = 8.5 Hz, 2H), 6.31 (d, J = 16.5 Hz, 1H), 6.27 (d, J = 16.0 Hz, 1H), 4.54 (s, 2H), 3.28 (s, 2H), 1.14 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 139.0, 138.9, 137.0, 131.6, 128.5, 127.8, 127.6, 125.9, 120.6, 79.3, 73.4, 38.1, 24.7; IR (film) v: 3030, 2959, 2925, 2858, 1547, 1532, 1460, 1308, 1249, 1198, 1016, 968, 909, 852, 806 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 21 BrO (M + ): 344.0776; Found: 344.0779. (E)-1-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-2-chlorobenzene (6f) Prepared following the Typical Procedure in 53% yield as a pale yellow liquid (32 mg, 0.107 mmol) for 6f, from (E)-1-chloro-2-(2-nitrovinyl)benzene 1g (37 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:100) as eluent. S18

Pale yellow liquid; R f = 0.41 (EtOAc/Petroleum ether 1:100); 1 H NMR (CDCl 3, 400MHz), δ: 7.54-7.31 (m, 1H), 7.36-7.32 (m, 5H), 7.31-7.28 (m, 1H), 7.22-7.18 (m, 1H), 7.16-7.12 (m, 1H), 6.79 (d, J = 16.4 Hz, 1H), 6.29 (d, J = 16.4 Hz, 1H), 4.56 (s, 2H), 3.32 (s, 2H), 1.19 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 141.0, 138.9, 136.1, 133.0, 129.7, 128.4, 128.1, 127.5, 126.84, 126.77, 123.4, 79.4, 73.4, 38.4, 24.7; IR (film) v: 3062, 3030, 2961, 2926, 2857, 1496, 1464, 1100, 1029, 744, 696 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 21 ClO (M + ): 300.1281; Found: 300.1282. (E)-2-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)phenol (6g) Prepared following the Typical Procedure in 50% yield as a pale yellow liquid (28 mg, 0.100 mmol) for 6g, from (E)-2-(2-nitrovinyl)phenol 1h (33 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:5) as eluent. S19

Yellow liquid; R f = 0.42 (EtOAc/Petroleum ether 1:5); 1 H NMR (CDCl 3, 400MHz), δ: 7.38-7.34 (m, 4H), 7.33-7.27 (m, 2H), 7.12-7.08 (m, 1H), 6.87 (t, J = 7.6 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 6.57 (d, J = 16.4 Hz, 1H), 6.19 (d, J = 16.4 Hz, 1H), 4.55 (s, 2H), 3.31 (s, 2H), 1.17 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 153.0, 140.6, 138.7, 128.5, 128.2, 127.67, 127.63, 127.5, 125.3, 121.5, 120.7, 115.9, 79.5, 73.5, 38.3, 24.6; IR (film) v: 3261, 3062, 3030, 2926, 1872, 1649, 1549, 1365, 1161, 942 cm -1 ; HRMS (EI) (m/z): calcd for C 19 H 22 O 2 (M + ): 282.1620; Found: 282.1623. (E)-4-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-1,2-dimethoxybenz ene (6h) Prepared following the Typical Procedure in 53% yield as a pale yellow liquid (34 mg, 0.104 mmol) for 6h, from (E)-1,2-dimethoxy-4-(2-nitrovinyl)benzene 1i (42 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:40) as eluent. S20

Pale yellow liquid; R f = 0.26 (EtOAc/Petroleum ether 1:40); 1 H NMR (CDCl 3, 400MHz), δ: 7.35-7.34 (m, 5H), 6.93-6.89 (m, 2H), 6.81 (d, J = 8.0 Hz, 1H), 6.32 (d, J = 16.4 Hz, 1H), 6.15 (d, J = 16.4 Hz, 1H), 4.56 (s, 2H), 3.91 (s, 3H), 3.88 (s, 3H), 3.29 (s, 2H), 1.16 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 149.1, 148.4, 139.0, 136.2, 131.1, 128.4, 127.54, 127.51, 126.6, 119.2, 111.2, 108.7, 79.6, 73.4, 56.0, 55.9, 37.9, 24.8; IR (film) v: 3058, 3029, 959, 2929, 2856, 1692, 1646, 1593, 1512, 1263, 1141, 1100, 1029, 967, 738, 701 cm -1 ; HRMS (EI) (m/z): calcd for C 21 H 26 O 3 (M + ): 326.1882; Found: 326.1880. (E)-2-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)furan (6i) Prepared following the Typical Procedure in 53% yield as a pale yellow liquid (39 mg, 0.152 mmol) for 6i, from (E)-2-(2-nitrovinyl)furan 1j (28 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:50) as eluent. S21

Pale yellow liquid; R f = 0.46 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 500MHz), δ: 7.34-7.27 (m, 6H), 6.35-6.34 (m, 1H), 6.25 (d, J = 16.5 Hz, 1H), 6.21 (d, J = 16.0 Hz, 1H), 6.16 (d, J = 3.0 Hz, 1H), 4.54 (s, 2H), 3.27 (s, 2H), 1.13 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 153.5, 141.4, 138.9, 137.0, 128.4, 127.6, 127.5, 116.0, 111.3, 106.7, 79.3, 73.4, 37.9, 24.6; IR (film) v: 3060, 3033, 2964, 2926, 2859, 1625, 1461, 1366, 1269, 1203, 1101, 1022, 803, 740, 703 cm -1 ; HRMS (EI) (m/z): calcd for C 17 H 20 O 2 (M + ): 256.1463; Found: 256.1454. (E)-2-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)thiophene (6j) Prepared following the Typical Procedure in 78% yield as a pale yellow liquid (42 mg, 0.154 mmol) for 6j, from (E)-2-(2-nitrovinyl)thiophene 1k (31 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:50) as eluent. S22

Pale yellow liquid; R f = 0.46 (EtOAc/Petroleum ether 1:50); 1 H NMR (CDCl 3, 500MHz), δ: 7.38-7.34 (m, 4H), 7.30-7.27 (m, 1H), 7.10 (d, J = 5.0 Hz, 1H), 6.95-6.93 (m, 1H), 6.90-6.89 (m, 1H), 6.51 (d, J = 16.5 Hz, 1H), 6.14 (d, J = 16.0 Hz, 1H), 4.55 (s, 2H), 3.27 (s, 2H), 1.14 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 143.5, 138.9, 138.0, 128.4, 127.6, 127.5, 127.4, 124.7, 123.4, 120.5, 79.2, 73.4, 38.0, 24.7; IR (film) v: 3063, 2959, 2924, 1640, 1607, 1457, 1420, 1259, 1201, 911, 800 cm -1 ; HRMS (EI) (m/z): calcd for C 17 H 20 OS (M + ): 272.1235; Found: 272.1236. (E)-3-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)pyridine (6k) Prepared following the Typical Procedure in 48% yield as a yellow liquid (25.6 mg, 0.095 mmol) for 6k, from (E)-3-(2-nitrovinyl)pyridine 1l (30 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:5) as eluent. S23

Yellow liquid; R f = 0.28 (EtOAc/Petroleum ether 1:5); 1 H NMR (CDCl 3, 400MHz), δ: 8.50 (d, J = 5.6 Hz, 2H), 7.68 (d, J = 8.0 Hz, 1H), 7.34-7.32 (m, 4H), 7.31-7.26 (m, 1H), 7.23-7.20 (m, 1H), 6.39-6.31 (m, 2H), 4.54 (s, 2H), 3.29 (s, 2H), 1.16 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 148.3, 148.1, 140.6, 138.8, 133.6, 132.7, 128.4, 127.60, 127.57, 123.49, 123.46, 79.2, 73.4, 38.2, 24.6; IR (film) v: 3030, 2962, 2927, 2859, 1568, 1532, 1100, 1025, 916, 737, 707 cm -1 ; HRMS (EI) (m/z): calcd for C 18 H 21 NO (M + ): 267.1623; Found: 267.1625. (E)-3-(4-(benzyloxy)-3,3-dimethylbut-1-en-1-yl)-1-tosyl-1H-indole (6l) Prepared following the Typical Procedure in 43% yield as a yellow liquid (39 mg, 0.085 mmol) for 6l, from (E)-3-(2-nitrovinyl)-1-tosyl-1H-indole 1m (69 mg, 0.2 mmol), (((2-methylallyl)oxy)methyl)benzene 2a (64.8 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:5) as eluent. S24

OBn N Ts 6l Yellow liquid; R f = 0.36 (EtOAc/Petroleum ether 1:5); 1 H NMR (CDCl 3, 400MHz), δ: 7.91 (d, J = 8.0 Hz, 1H), 7.67 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.4 Hz, 1H), 7.46 (s, 1H), 7.25-7.16 (m, 7H), 7.11 (d, J = 8.0 Hz, 2H), 6.35 (d, J = 16.4 Hz, 1H), 6.27 (d, J = 16.4 Hz, 1H), 4.47 (s, 2H), 3.22 (s, 2H), 2.23 (s, 3H), 1.09 (s, 6H); 13 C NMR (CDCl 3, 100MHz), δ: 145.0, 139.7, 138.9, 135.6, 135.3, 130.0, 129.5, 128.4, 127.6, 127.0, 124.9, 123.4, 123.1, 121.2, 120.6, 117.4, 113.8, 79.4, 73.4, 38.3, 24.7, 21.7; IR (film) v: 3057, 2962, 2925, 2857, 1548, 1450, 1370, 1269, 1175, 1124, 1096, 1025, 741, 704, 578 cm -1 ; HRMS (EI) (m/z): calcd for C 28 H 29 NO 3 S (M + ): 459.1868; Found: 459.1869. (S,E)-7-(3,4-dimethoxyphenyl)-3,5,5-trimethylhept-6-en-1-ol (6m) Prepared following the Typical Procedure in 54% yield as a yellow liquid (34 mg, 0.106 mmol) for 6m, from (E)-1,2-dimethoxy-4-(2-nitrovinyl)benzene 1i (42 mg, 0.2 mmol), (S)-(-)-β-Citronellol 2m (62 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:3) as eluent. S25

Pale yellow liquid; R f = 0.26 (EtOAc/Petroleum ether 1:3); 1 H NMR (CDCl 3, 400MHz), δ: 6.92-6.88 (m, 2H), 6.81 (d, J = 8.0 Hz, 1H), 6.20 (d, J = 16.0 Hz, 1H), 6.03 (d, J = 16.4 Hz, 1H), 3.91 (s, 3H), 3.87 (s, 3H), 3.69-3.64 (m, 2H), 1.60 (s, 1H), 1.36-1.21 (m, 9H), 1.08 (s, 6H), 0.87 (d, J = 6.4 Hz, 3H); 13 C NMR (CDCl 3, 100MHz), δ: 149.1, 148.3, 139.1, 131.4, 125.4, 118.9, 111.3, 108.8, 61.4, 56.1, 56.0, 43.7, 40.1, 38.0, 36.4, 29.6, 27.48, 27.45, 22.2, 19.8; IR (film) v: 3460, 2935, 1593, 1546, 1513, 1413, 1262, 1143, 1089, 1027, 969, 863, 805 cm -1 ; HRMS (EI) (m/z): calcd for C 20 H 32 O 3 (M + ): 320.2351; Found: 320.2351. 3-((E)-4-(((1R,2S,5R)-2-isopropyl-5-methylcyclohexyl)oxy)-3,3-dim ethylbut-1-en-1-yl)pyridine (6n) Prepared following the Typical Procedure in 63% yield as a yellow liquid (40 mg, 0.127 mmol) for 6n, from (E)-3-(2-nitrovinyl)pyridine 1l (30 mg, 0.2 mmol), (1S,2R,4R)-1-isopropyl-4-methyl-2-((2-methylallyl)oxy)cyclohexane 2n (83 mg, 0.4 mmol), Fe(acac) 3 (7.2 mg, 10 mol %), PhSiH 3 (43.2 mg, 0.4 mmol) in 2 ml EtOH for 8 h at 60 o C. The purification was performed by flash column chromatography on silica gel using ethyl acetate/petroleum ether (v/v, 1:5) as eluent. S26

Pale yellow liquid; R f = 0.28 (EtOAc/Petroleum ether 1:5); 1 H NMR (CDCl 3, 400MHz), δ: 8.55 (s, 1H), 8.41 (d, J = 4.0 Hz, 1H), 7.66 (dt, J 1 = 8.0 Hz, J 2 = 1.6 Hz, 1H), 7.21 (dd, J 1 = 7.6 Hz, J 2 = 4.8 Hz,, 1H), 6.37 (d, J = 16.4 Hz, 1H), 6.32 (d, J = 16.4 Hz, 1H), 3.46 (d, J = 8.4 Hz, 1H), 3.06 (d, J = 8.8 Hz, 1H), 2.99 (td, J 1 = 10.4 Hz, J 2 = 4.0 Hz, 1H), 2.26-2.21 (m, 1H), 2.10-2.05 (m, 1H), 1.87 (s, 1H), 1.65-1.57 (m, 2H), 1.33-1.21 (m, 2H), 1.13 (s, 3H), 1.12 (s, 3H), 0.96-0.92 (m, 1H), 0.90 (d, J = 6.4 Hz, 3H), 0.86 (d, J = 7.2 Hz, 3H), 0.84-0.81 (m, 1H), 0.72 (d, J = 6.8 Hz, 3H); 13 C NMR (CDCl 3, 100MHz), δ: 148.3, 148.0, 141.1, 133.7, 132.6, 123.5, 123.3, 79.9, 77.8, 48.4, 40.3, 38.3, 34.8, 31.7, 25.8, 24.7, 24.6, 23.5, 22.5, 21.1, 16.3; IR (film) v: 3029, 2954, 2922, 2866, 1676, 1646, 1565, 1462, 1421, 1371, 1313, 1236, 1179, 1099, 1018, 922, 849 cm -1 ; HRMS (EI) (m/z): calcd for C 21 H 33 NO (M + ): 315.2562; Found: 315.2566. 4. Radical Scavenger Test A Schlenk tube containing (E)-(2-nitrovinyl)benzene (15 mg, 0.1 S27

mmol), Fe(acac) 3 (3.56 mg, 10 mol %), TEMPO (31 mg, 0.2 mmol) were evacuated and purged with Argon three times. Afterwards, (((2-methylallyl)oxy)methyl)benzene (32.4 mg, 0.2 mmol), PhSiH 3 (21.6 mg, 0.2 mmol) and 1 ml EtOH was added via syringe. The solution was kept at 60 o C for 8 h. The conversion was very low (< 10%). Replacing TEMPO with BHT gave the same result. S28

S29

S30

Ph OPh 3b CDCl 3, 400MHz S31

Ph OPh 3b CDCl 3,100MHz S32

S33

S34

S35

S36

Ph N 3e CDCl 3, 400MHz Boc S37

Ph N 3e CDCl 3, 100MHz Boc S38

S39

S40

S41

S42

S43

S44

S45

S46

S47

S48

S49

S50

S51

S52

OBn Me 6a CDCl 3, 400MHz S53

OBn Me 6a CDCl 3, 100MHz S54

S55

S56

OBn Me 2 N 6c CDCl 3, 400MHz S57

OBn Me 2 N 6c CDCl 3, 100MHz S58

S59

S60

S61

S62

S63

S64

S65

S66

5.30 7.335 7.337 7.341 7.349 7.260 2.03 0.97 6.798 6.818 6.888 6.893 6.914 6.927 6.931 1.00 6.340 6.299 1.00 6.175 6.134 S67

S68

S69

S70

OBn S 6j CDCl 3, 500MHz S71

OBn S 6j CDCl 3, 100MHz S72

S73

S74

8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 f1 (ppm) 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 S75

S76

S77

S78

S79

S80