Solvent-Controlled Pd(II)-Catalyzed Aerobic Chemoselective. Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination of

Supporting Information Solvent-Controlled Pd(II)-Catalyzed Aerobic Chemoselective Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination of Conjugated Dienes for the Synthesis of Functionalized 1,4-Benzoxazines Ke Wen, Zhengxing Wu, Banruo Huang, Zheng Ling, Ilya D. Gridnev, and Wanbin Zhang*, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P.R. China Department of Chemistry, Graduate School of Science, Tohoku University, Aramaki 3-6, Aoba-ku, Sendai 980-8578, Japan CONTENTS 1. GENERAL DETAILS... S1 2. PREPARATION OF PROTECTED O-AMINOPHENOL SUBSTRATES... S1 3. PD(II)-CATALYZED AEROBIC CHEMOSELECTIVE INTERMOLECULAR 1,2-AMINOOXYGENATION AND 1,2-OXYAMINATION... S10 4. TRANSFORMATIONS... S32 5. PRELIMINARY MECHANISM STUDY... S35 5.1. IN SITU 1 H NMR SPECTROSCOPY... S35 5.2. HRMS STUDIES... S43 5.3. PROPOSED CATALYTIC CYCLE OF 1,2-AMINOOXYGENATION AND 1,2-OXYAMINATION... S45 6. NMR SPECTRA... S47 7. X-RAY CRYSTAL STRUCTURE ANALYSIS... S125 8. REFERENCES... S130 S0

1. General Details All reactions were performed in glassware or pressure vessel, and the workup was operated in air, unless otherwise noted. The solvent N, N-dimethylformamide (DMF), 1,2-dimethoxyethane (DME), 1,4-dioxane, toluene, tetrahydrofuran (THF), methanol (MeOH), 1,2-dichloroethane (DCE), acetonitrile (MeCN) and dimethyl sulfoxide (DMSO), were distilled over dehydrating reagents. The commercially available reagents were used without further purification. 1,3-Butadiene 2b was purified via distillation at low temperature. Conjugated dienes 2d and 2g were prepared according to literature. [1] The purification of products with column chromatography was carried out using silica gel (100~200 mesh). The NMR spectra were recorded on Bruker Advance III HD 400 (400 MHz, 1 H; 100 MHz, 13 C) dealed with the software MestReNova. HRMS was performed on a Waters Micromass Q-TOF Premier Mass Spectrometer at the Instrumental Analysis Center of Shanghai Jiao Tong University. Melting points were measured with SGW X-4 micro melting point apparatus. X-Ray crystallography data were collected using an Xcalibur Atlas Gemini ultra diffractometer. 2. Preparation of Protected o-aminophenol Substrates N-(2-Hydroxyphenyl)-4-methylbenzenesulfonamide (1a) [2] o-aminophenol (1.00 g, 9.2 mmol, 1 equiv) was dissolved in pyridine (15 ml), then 4-toluene sulfonyl chloride (5.26 g, 27.5 mmol, 3 equiv) was added portionwise to the mixture and the reaction mixture was stirred at 60 o C for 24 h. Then the reaction mixture was cooled to room temperature, extracted with 30 ml of ethyl acetate and washed three times with diluted HCl solution, once with saturated NaHCO 3 and three times with saturated NaCl. The organic layer was combined and dried over Na 2 SO 4, filtered, and concentrated under reduced pressure. Recrystallization with petroleum ether S1

and ethyl acetate gave the di-ts protected o-aminophenol (3.64 g, 95% yield), which was used in the next step without further purification. The di-ts protected o-aminophenol (1.00 g, 2.4 mmol, 1 equiv) was dissolved in 30 ml MeOH, then Mg (0.58 g, 10 equiv) was added to the mixture in one portion. The resulting mixture was stirred at 40 o C for 12 h. The reaction mixture was then cooled to room temperature, extracted with 30 ml of ethyl acetate and washed with diluted HCl solution for three times and saturated NaCl once. The organic layer was combined and dried over Na 2 SO 4. The solvent was removed under reduced pressure. Purification by column chromatography on silica gel (petroleum ether/etoac = 5/1) gave product in 87% yield (1a, 550.0 mg). Known compound: 1 H NMR (400 MHz, CDCl 3 ) δ 7.62 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.09-7.01 (m, 1H), 6.89 (dd, J = 8.1, 1.3 Hz, 1H), 6.84 (dd, J = 7.9, 1.6 Hz, 1H), 6.76-6.70 (m, 1H), 6.63 (s, 1H), 6.51 (s, 1H), 2.38 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.5, 144.5, 135.1, 129.9, 128.2, 127.7, 125.6, 123.2, 121.2, 117.1, 21.8. N-(2-Hydroxy-4-methylphenyl)-4-methylbenzenesulfonamide (1b) Using the same method and molar quatity as 1a, the product 1b was obtained as a white solid (512.5 mg, 77% yield). Mp = 106~107 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 6.71 (d, J = 1.6 Hz, 1H), 6.67-6.62 (m, 2H), 6.50 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 2.38 (s, 3H), 2.21 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 150.9, 144.4, 138.9, 135.1, 129.8, 127.8, 125.9, 121.8, 120.2, 117.7, 21.8, 21.3. HRMS (ESI) calcd for C 14 H 16 NO 3 S [M+H] + 278.0851, found 278.0855. N-(4-Ethyl-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1c) Using the same method and molar quantity as 1a, the product 1c was obtained as a yellow solid (566.4 mg, 81% yield). Mp = 98~99 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H), 6.75 (d, J = 9.2 Hz, 2H), 6.82-6.66 (m, 4H), 2.50 (q, J = 7.6 Hz, 2H), 2.37 (s, 3H), S2

1.14 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.8, 145.1, 144.4, 135.2, 129.8, 127.7, 125.8, 120.5, 120.4, 116.4, 28.6, 21.8, 15.4. HRMS (ESI) calcd for C 15 H 18 NO 3 S [M+H] + 292.1007, found 292.0995. N-(2-Hydroxy-4-methoxyphenyl)-4-methylbenzenesulfonamide (1d) Using the same method and molar quantity as 1a, the product 1d was obtained as a red solid (443.5 mg, 63% yield). Mp = 149~150 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.59 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 6.71 (s, 1H), 6.52 (d, J = 2.8 Hz, 1H), 6.43 (d, J = 8.8 Hz, 1H), 6.23 (dd, J = 8.8, 2.4 Hz, 1H), 6.17 (s, 1H), 3.74 (s, 3H), 2.41 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 154.0, 144.6, 134.7, 129.9, 128.5, 127.9, 114.9, 110.0, 107.2, 102.5, 55.7, 21.9. HRMS (ESI) calcd for C 14 H 15 NNaO 4 S [M+Na] + 316.0619, found 316.0612. N-(4-Fluoro-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1e) Using the same method and molar quantity as 1a, the product 1e was obtained as a yellow solid (378.1 mg, 56% yield). Mp = 130~131 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.59 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 6.73 (br, 1H), 6.69 (dd, J = 9.6, 2.8 Hz, 1H), 6.53 (dd, J = 8.8, 6.0 Hz, 1H), 6.41 (td, J = 8.4, 2.8 Hz, 1H), 6.14 (s, 1H), 2.42 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 162.4 (d, J = 245.7 Hz), 153.5 (d, J = 12.7 Hz), 144.6, 134.3, 129.8, 128.0 (d, J = 10.4 Hz), 127.6, 118.4 (d, J = 3.2 Hz), 107.8 (d, J = 22.8 Hz), 104.9 (d, J = 25.5 Hz), 21.7. HRMS (ESI) calcd for C 13 H 13 FNO 3 S [M+H] + 282.0600, found 282.0613. N-(4-Chloro-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1f) Using the same method and molar quantity as 1a, the product 1f was obtained as a gray solid (557.4 mg, 78% yield). Mp = 133~134 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 8.4 Hz, 2H), S3

7.24 (d, J = 8.0 Hz, 2H), 6.91 (d, J = 2.0 Hz, 1H), 6.82 (s, 1H), 6.78-6.61 (m, 3H), 2.40 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 151.3, 144.6, 134.6, 133.2, 129.8, 127.5, 126.3, 121.7, 121.1, 117.3, 21.6. HRMS(ESI) calcd for C 13 H 13 ClNO 3 S [M+H] + 298.0305, found 298.0298. N-(4-Bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1g) Using the same method and molar quantity as 1a, the product 1g was obtained as a white solid (624.2 mg, 76% yield). Mp = 126~127 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 2.0 Hz, 1H), 6.87-6.79 (m, 2H), 6.70 (d, J = 8.4 Hz, 1H), 6.67 (s, 1H), 2.40 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 151.3, 144.8, 134.7, 130.0, 127.7, 126.5, 124.2, 122.5, 120.9, 120.4, 21.9. HRMS (ESI) calcd for C 13 H 13 BrNO 3 S [M+H] + 341.9800, found 341.9800. N-(2-Hydroxy-4-(trifluoromethyl)phenyl)-4-methylbenzenesulfonamide (1h) Using the same method and molar quantity as 1a, the product 1h was obtained as a white solid (397.6 mg, 50% yield). Mp = 122~123 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.66 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 7.15-7.07 (m, 2H), 7.03 (d, J = 8.4 Hz, 1H), 6.85 (s, 1H), 6.63 (s, 1H), 2.40 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 153.9, 143.6, 137.8, 129.9, 127.2, 125.3, 124.8 (q, J = 269.3 Hz), 123.7 (q, J = 3.8 Hz), 121.5 (q, J = 3.8 Hz), 119.8 (q, J = 31.9 Hz), 116.3, 21.4. HRMS (ESI) calcd for C 14 H 13 F 3 NO 3 S [M+H] + 332.0568, found 332.0570. N-(2-Hydroxy-5-methylphenyl)-4-methylbenzenesulfonamide (1i) Using the same method and molar quantity as 1a, the product 1i was obtained as a white solid (585.7 mg, 88% yield). Mp = 135~136 C; 1 H NMR (400 MHz, DMSO) δ 9.29 (s, 1H), 9.07 (s, 1H), 7.62 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 2.0 Hz, 1H), 6.72 (dd, J = 8.4, 2.0 Hz, 1H), 6.60 (d, J = 8.0 Hz, 1H), 2.33 (s, 3H), 2.12 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 148.4, 143.4, S4

138.4, 129.9, 128.1, 127.4, 127.2, 125.6, 124.5, 115.9, 21.6, 20.9. HRMS (ESI) calcd for C 14 H 16 NO 3 S [M+H] + 278.0848, found 278.0855. N-(5-(Tert-butyl)-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1j) Using the same method and molar quantity as 1a, the product 1j was obtained as a white solid (559.6 mg, 73% yield). Mp = 94~95 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.59 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 7.06 (dd, J = 8.4, 2.4 Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 6.63 (d, J = 2.4 Hz, 1H), 6.55 (s, 1H), 6.43 (br, 1H), 2.37 (s, 3H), 1.08 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 148.8, 144.5, 144.1, 134.8, 129.7, 128.0, 125.3, 123.4, 122.2, 116.6, 34.1, 31.4, 21.7. HRMS (ESI) calcd for C 17 H 22 NO 3 S [M+H] + 320.1320, found 320.1311. N-(2-Hydroxy-5-nitrophenyl)-4-methylbenzenesulfonamide (1k) [3] 2-Amino-4-nitrophenol (1.00 g, 6.5 mmol, 1 equiv) and pyridine (0.6 ml, 7.2 mmol, 1.1 equiv) was added to 15 ml CH 2 Cl 2 and the mixture was cooled to 0 o C. Then 4-toluene sulfonyl chloride (1.24 g, 6.5 mmol, 1 equiv) was added to the mixutre in one portion. After the addition, the reaction was warmed to room temperature and stirred for 5 h. Diluted HCl solution was then added to the mixure to make a yellow precipate, which was then washed with CH 2 Cl 2 and H 2 O to give the product in 70% yield (1k, 1.40 g). A yellow solid. Known compound: 1 H NMR (400 MHz, DMSO) δ 8.06 (d, J = 2.8 Hz, 1H), 7.89 (dd, J = 9.0, 2.8 Hz, 1H), 7.66 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 6.88 (d, J = 9.0 Hz, 1H), 2.34 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 157.2, 144.0, 139.7, 137.8, 130.2, 127.4, 125.7, 123.0, 119.7, 115.9, 21.7. N-(2-Hydroxy-5-methoxyphenyl)-4-methylbenzenesulfonamide (1k') S5

Using the same method and molar quantity as 1a, the product 1k' was obtained as a red solid (415.3 mg, 59% yield). Mp = 115~116 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.64 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 6.78 (d, J = 8.8 Hz, 1H), 6.72 (s, 1H), 6.58 (dd, J = 8.8, 2.8 Hz, 1H), 6.54 (d, J = 2.8 Hz, 1H), 5.96 (s, 1H), 3.62 (s, 3H), 2.38 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 153.9, 144.5, 143.4, 135.3, 129.9, 127.7, 124.1, 117.5, 113.0, 110.0, 56.0, 21.8. HRMS (ESI) calcd for C 14 H 15 NNaO 4 S [M+Na] + 316.0619, found 316.0590. N-(5-Fluoro-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1l) Using the same method and molar quantity as 1a, the product 1l was obtained as a red solid (330.8 mg, 49% yield). Mp = 137~138 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.65 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 6.83-6.67 (m, 4H), 6.12 (br, 1H), 2.40 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.6 (d, J = 238.2 Hz), 145.0 (d, J = 2.7 Hz), 144.5, 135.0, 129.8, 127.4, 124.2 (d, J = 10.3 Hz), 117.0 (d, J = 8.9 Hz), 113.4 (d, J = 22.9 Hz), 110.8 (d, J = 26.0 Hz), 21.6. HRMS (ESI) calcd for C 13 H 13 FNO 3 S [M+H] + 282.0600, found 282.0575. N-(5-Chloro-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1m) [4] 2-Amino-4-chlorophenol (1.00 g, 7.0 mmol, 1 equiv) was added to 15 ml CH 2 Cl 2 and the mixture was cooled to 0 o C. Then a mixure of 4-toluene sulfonyl chloride (1.3 g, 7.0 mmol, 1 equiv) and triethylamine (1.1 ml, 7.7 mmol, 1.1 equiv) in 10 ml CH 2 Cl 2 was added dropwise in 10 minutes. After the addition, the reaction was warmed to room temperature and stirred for 3 h. The mixture was then washed with 20 ml of H 2 O and the organic layer was collected and dried over Na 2 SO 4. Removal of solvent under reduced pressure gave the crude product. Recrystalization from PE/EA to give the O-Ts protected product (1.83 g, 88% yield), which was then used in the next step without further purification. Under inert atmosphere, the O-Ts-protected product (1.00 g, 3.4 mmol, 1 equiv) was dissolved in 20 ml dried THF and the mixture was cooled to -78 o C. n-butyllithium (2.5 mol/l THF solution, 5.38 S6

ml, 4 equiv) was then added to the mixture dropwise in 15 min. The resulting mixture was stirred at -78 o C for 1.5 h and warmed to room temperature slowly. Saturated NH 4 Cl solution was added in order to quench the reaction. The mixture was then extracted with 30 ml EA and washed with saturated NaCl once. The organic phase was dried over Na 2 SO 4. Removal of solvent under reduced pressure gave the crude product. Purification by column chromatography on silica gel (petroleum ether/etoac = 5/1) gave product in 61% yield (1m, 617.6 mg). A deep yellow solid. Known compound: 1 H NMR (400 MHz, CD 3 OD) δ 7.64 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 2.4 Hz, 1H), 7.24 (d, J = 8.4 Hz, 2H), 6.87 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 6.63 (d, J = 8.4 Hz, 1H), 2.35 (s, 3H). 13 C NMR (100 MHz, CD 3 OD) δ 148.3, 143.9, 136.9, 129.2, 127.2, 126.0, 125.3, 123.7, 123.0, 115.9, 20.3. N-(5-Bromo-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1n) Using the same method and molar quantity as 1a, the product 1n was obtained as a white solid (525.6 mg, 64% yield). Mp = 180~181 C; 1 H NMR (400 MHz, CD 3 OD) δ 7.64 (d, J = 8.0 Hz, 2H), 7.44 (d, J = 2.4 Hz, 1H), 7.26 (d, J = 7.6 Hz, 2H), 7.01 (dd, J = 8.6 Hz, 2.4 Hz, 1H), 6.59 (d, J = 8.4 Hz, 1H), 2.36 (s, 3H). 13 C NMR (100 MHz, CD 3 OD) δ 148.8, 143.9, 136.9, 129.2, 128.3, 127.2, 126.4, 125.9, 116.4, 110.4, 20.3. HRMS (ESI) calcd for C 13 H 13 BrNO 3 S [M+H] + 341.9800, found 341.9796. N-(2-Hydroxy-5-(trifluoromethyl)phenyl)-4-methylbenzenesulfonamide (1o) Using the same method and molar quantity as 1a, the product 1o was obtained as a white solid (381.7 mg, 48% yield). Mp = 153~154 C; 1 H NMR (400 MHz, DMSO) δ 10.57 (br, 1H), 9.62 (br, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 2.0 Hz, 1H), 7.31 (d, J = 8.4 Hz, 2H), 7.27 (dd, J = 10.0 Hz, 2.0 Hz, 1H), 6.86 (d, J = 8.4 Hz, 1H), 2.32 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 153.9, 143.6, 137.8, 129.9, 127.2, 125.3, 124.8 (q, J = 269.3 Hz), 123.4 (q, J = 3.8 Hz), 121.5 (q, J = 3.8 Hz), 119.8 (q, J = 31.9 Hz), 116.3, 21.4. HRMS (ESI) calcd for C 14 H 13 F 3 NO 3 S [M+H] + 332.0568, found 332.0555. N-(2-Hydroxy-4,5-dimethylphenyl)-4-methylbenzenesulfonamide (1p) [5] S7

2-Amino-4,5-dimethylphenol (1.00 g, 7.3 mmol, 1 equiv) and pyridine (0.65 ml, 8.0 mmol, 1.1 equiv) was added to 15 ml CH 2 Cl 2. Then 4-toluene sulfonyl chloride (1.40 g, 7.3 mmol, 1 equiv) was added to the mixutre in one portion. After the addition, the reaction was stirred for 2 h at room temperature. The mixture was then washed with 20 ml of H 2 O and the organic layer was collected and dried over Na 2 SO 4. Removal of solvent under reduced pressure gave the crude product. Purification by column chromatography on silica gel (petroleum ether/etoac = 5/1) gave product in 50% yield (1p, 1.06 g). A light purple solid. Known compound: 1 H NMR (400 MHz, CDCl 3 ) δ 7.61 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 6.68 (s, 1H), 6.53 (s, 2H), 6.32 (s, 1H), 2.39 (s, 3H), 2.12 (s, 3H), 2.00 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 148.8, 144.3, 137.2, 135.2, 129.8, 129.2, 127.7, 127.0, 120.0, 118.3, 21.8, 19.8, 19.0. N-(4,5-Dichloro-2-hydroxyphenyl)-4-methylbenzenesulfonamide (1q) Using the same method and molar quantity as 1p, the product 1q was obtained as a yellow solid (776.0 mg, 32% yield). Mp = 126~127 C; 1 H NMR (400 MHz, DMSO) δ 10.45 (s, 1H), 9.66 (s, 1H), 7.64 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 7.30 (s, 1H), 6.89 (s, 1H), 2.35 (s, 3H). 13 C NMR (100 MHz, DMSO) δ 150.6, 143.9, 137.9, 130.2, 127.9, 127.4, 125.7, 125.6, 120.7, 117.2, 21.7. HRMS (ESI) calcd for C 13 H 12 Cl 2 NO 3 S [M+H] + 331.9915, found 331.9928. N-(2-Hydroxy-6-methylphenyl)-4-methylbenzenesulfonamide (1r) Using the same method and molar quantity as 1a, the product 1r was obtained as a white solid (406.0 mg, 61% yield). Mp = 122~123 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.58 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.21 (s, 1H), 7.05 (t, J = 7.8 Hz, 1H), 6.88 (d, J = 8.0 Hz, 1H), 6.59 (d, J = 7.6 Hz, 1H), 6.34 (s, 1H), 2.41 (s, 3H), 1.62 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 154.3, 145.3, 136.9, S8

135.6, 130.5, 129.7, 128.1, 123.2, 121.6, 116.5, 22.4, 18.2. HRMS (ESI) calcd for C 14 H 16 NO 3 S [M+H] + 278.0848, found 278.0840. N-(3-Hydroxynaphthalen-2-yl)-4-methylbenzenesulfonamide (1s) Using the same method and molar quantity as 1a, the product 1s was obtained as a yellow solid (503.9 mg, 67% yield). Mp = 166~167 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.68 (d, J = 8.4 Hz, 2H), 7.65-7.55 (m, 3H), 7.39-7.33 (m, 1H), 7.32-7.27 (m, 1H), 7.22-7.12 (m, 3H), 7.05 (s, 1H), 6.36 (br, 1H), 2.34 (s, 3H). 13 C NMR (100MHz, CDCl 3 ) δ 146.6, 144.4, 135.5, 132.2, 129.9, 129.0, 127.7, 127.6, 126.3, 126.2, 125.4, 124.5, 120.7, 111.0, 21.8. HRMS (ESI) calcd for C 17 H 16 NO 3 S [M+H] + 314.0844, found 314.0850. S9

3. Pd(II)-Catalyzed Aerobic Chemoselective Intermolecular 1,2-Aminooxygenation and 1,2-Oxyamination General procedure with Method A: To a sealed tube (15 ml) were added substrate 1 (0.1 mmol, 1 equiv), Pd(OAc) 2 (2.2 mg, 0.1 equiv), followed by the solvent MeCN (1 ml). Afterwards, the system was degassed and recharged with O 2 balloon three times. Finally, the conjugated diene 2 (detailed equivalents are mentioned in the manuscript) was added and the tube was sealed and heated to 70 o C. After stirring for 24 h, the reaction mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was purified by preparative TLC on silica gel (normal ratio: petroleum ether/etoac = 5/1) to give the product 3. General procedure with Method B: To a sealed tube (15 ml) were added substrate 1 (0.1 mmol, 1 equiv), Pd(OAc) 2 (2.2 mg, 0.1 equiv), 2,5-dimethyl-BQ (0.2 mmol, 2 equiv), followed by the solvent DMSO (1 ml). Afterwards the system was degassed and recharged with O 2 (balloon) three times. Finally, the conjugated diene 2 (detailed equivalents are mentioned in the manuscript) was added and the reaction mixture was heated to 70 o C. After stirring for a certain time, the reaction mixture was cooled to room temperature, the mixture was purified by preparative TLC on silica gel (normal ratio: petroleum ether/etoac = 5/1) to give the product 4. S10

Table S1. Optimization of the reaction conditions a a The reaction was carried out with 1a (0.1 mmol, 1 equiv), 2a (1 mmol, 10 equiv) and oxidant (0.2 mmol, 2 equiv) in solvent (1 ml), in the presence of Pd(OAc) 2 (10 mol %) at 70 o C for 24 h unless otherwise noted. b Isolated yields of the two chemoselective products. c The ratios were determined by 1 H NMR analysis. We also tried the dienes 2g and 2h as the extension of diene scope, and the corresponding products with moderate or low yields were obtained. The results are shown in Table S2. Table S2. Scope of conjugated dienes. a a Isolated yields of the two chemoselective products. The ratio was determined by 1 H NMR analysis. b Using diene 2g (3 equiv) and O 2 (20 atm.). c Pd(OAc) 2 (0.2 equiv), diene 2h (5 equiv) and O 2 (20 atm.) were used in Method A; Pd(OAc) 2 (0.2 equiv), diene 2h (5 equiv), BQ (2 equiv, replaced 2,5-dimethyl-BQ) and O 2 (20 atm.) used in Method B. S11

Scale-up of the reaction To a sealed tube (100 ml) were added substrate 1a (316.0 mg, 1.2 mmol, 1 equiv) and Pd(OAc) 2 (26.9 mg, 10 mol%), followed by the solvent MeCN (3 ml). Afterwards, the system was degassed and recharged with O 2 balloon three times. Finally, isoprene 2a (817.2 mg, 10 equiv) was added and the tube was sealed and heated to 70 o C. After stirring for 24 h, the reaction mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was purified by column chromatography on silica gel (petroleum ether/etoac = 5/1) to give the product as a white solid (332.0 mg, 84% yield, 3a:4a = 9:1). To a sealed tube (100 ml) were added substrate 1a (316.0 mg, 1.2 mmol, 1 equiv), Pd(OAc) 2 (26.9 mg, 10 mol%) and 2,5-dimethyl-BQ (326.8 mg, 2.4 mmol, 2 equiv), followed by the solvent DMSO (3 ml). Afterwards, the system was degassed and recharged with O 2 balloon three times. Finally, isoprene 2a (817.2 mg, 10 equiv) was added and the tube was sealed and heated to 70 o C. After stirring for 24 h, the reaction mixture was cooled to room temperature. The mixture was purified by column chromatography on silica gel (petroleum ether/etoac = 5/1) to give the product as a white solid (237.1 mg, 60% yield, 4a:3a > 20:1). S12

2-(Prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3a) White solid (30.3 mg, 92% yield). Mp = 121~122 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (dd, J = 8.4, 1.6 Hz, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.12-7.06 (m, 1H), 6.98-6.92 (m, 1H), 6.87 (dd, J = 8.4, 1.6 Hz, 1H), 5.00-4.95 (m, 2H), 4.30 (dd, J = 14.4, 2.4 Hz, 1H), 3.58 (dd, J = 10.0, 1.6 Hz, 1H), 3.13 (dd, J = 14.4, 10.4 Hz, 1H), 2.39 (s, 3H), 1.71 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ147.3, 144.6, 140.6, 135.7, 130.1, 127.5, 126.5, 125.0, 123.5, 121.1, 117.7, 114.0, 74.2, 48.1, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 20 NO 3 S [M+H] + 330.1164, found 330.1168. 7-Methyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3b) White solid (32.3 mg, 94% yield). Mp = 96~97 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.74 (d, J = 8.4 Hz, 1H), 7.51 (d, J = 7.6 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 6.77 (d, J = 8.4 Hz, 1H), 6.68 (s, 1H), 4.99-4.92 (m, 2H), 4.27 (dd, J = 14.4, 2.4 Hz, 1H), 3.50 (dd, J = 10.4, 1.6 Hz, 1H), 3.09 (dd, J = 14.8, 10.4 Hz, 1H), 2.39 (s, 3H), 2.29 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ147.1, 144.5, 140.7, 136.7, 135.6, 130.1, 127.5, 125.0, 122.0, 120.8, 117.9, 113.9, 74.0, 48.1, 21.8, 21.1, 18.4. HRMS (ESI) calcd for C 19 H 22 NO 3 S [M+H] + 344.1320, found 344.1308. 7-Ethyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3c) White solid (34.7 mg, 97% yield). Mp = 71~72 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 8.8 Hz, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.24 (d,j = 8.4 Hz, 2H), 6.79 (dd, J = 8.4, 1.6 Hz, 1H), 6.71 (d, J = 1.6 Hz,1H), 4.99-4.93 (m, 2H), 4.26 (dd, J = 14.8, 2.4 Hz, 1H), 3.52 (dd, J = 10.4, 1.6 Hz, 1H), 3.10 (dd, J = 14.6, 10.0 Hz, 1H), 2.59 (q, J = 7.6 Hz, 2H), 2.39 (s, 3H), 1.69 (s, 3H), 1.21 (t, J = 7.2 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.1, 144.5, 143.0, 140.7, 135.6, 130.1, 127.5, 125.0, 121.0, 121.0, S13

116.6, 113.9, 74.1, 48.1, 28.4, 21.8, 18.4, 15.4. HRMS (ESI) calcd for C 20 H 24 NO 3 S [M+H] + 358.1477, found 358.1464. 7-Methoxy-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3d) White solid (25.5 mg, 71% yield). Mp = 68~69 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J = 9.2 Hz, 1H), 7.48 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.56 (dd, J = 9.2, 2.8 Hz, 1H), 6.40 (d, J = 2.8 Hz, 1H), 4.99-4.91 (m, 2H), 4.26 (dd, J = 14.8, 2.4 Hz, 1H), 3.77 (s, 3H), 3.47 (dd, J = 10.4, 2.0 Hz, 1H), 3.08 (dd, J = 14.8, 10.4 Hz, 1H), 2.39 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.4, 148.4, 144.5, 140.6, 135.5, 130.1, 127.6, 126.6, 116.5, 114.0, 108.0, 101.9, 74.0, 55.6, 48.1, 21.8, 18.4. HRMS (ESI) calcd for C 19 H 22 NO 4 S [M+H] + 360.1270, found 360.1251. 7-Fluoro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3e) White solid (25.0 mg, 72% yield). Mp = 104~105 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.83 (dd, J = 9.2, 6.0 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 6.69 (ddd, J = 9.2, 8.0, 3.2 Hz, 1H), 6.59 (dd, J = 9.2, 2.8 Hz, 1H), 5.00-4.92 (m, 2H), 4.28 (dd, J = 14.8, 2.4 Hz, 1H), 3.50 (dd, J = 10.4, 2.0 Hz, 1H), 3.09 (dd, J = 14.8, 10.4 Hz, 1H), 2.40 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.9 (d, J = 243.4 Hz), 148.4(d, J = 12.4 Hz), 144.8, 140.2, 135.3, 130.2, 127.5, 126.5 (d, J = 9.6 Hz), 119.6 (d, J = 3.0 Hz), 114.2, 108.3 (d, J = 22.6 Hz), 104.6 (d, J = 25.5 Hz), 74.3, 47.8, 21.8, 18.3. HRMS (ESI) calcd for C 18 H 19 FNO 3 S [M+H] + 348.1070, found 348.1071. 7-Chloro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3f) S14

White solid (26.9 mg, 74% yield). Mp = 101~102 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (d, J = 8.8 Hz, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.4 Hz, 2H), 6.93 (dd, J = 8.8, 2.4 Hz, 1H), 6.89 (d, J = 2.4 Hz, 1H), 5.01-4.92 (m, 2H), 4.28 (dd, J = 14.8, 2.4 Hz, 1H), 3.51 (dd, J = 10.4, 2.0 Hz, 1H), 3.09 (dd, J = 14.8, 10.4 Hz, 1H), 2.41 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ147.8, 144.9, 140.1, 135.3, 131.5, 130.2, 127.5, 126.0, 122.3, 121.3, 117.8, 114.3, 74.3, 47.8, 21.8, 18.3. HRMS (ESI) calcd for C 18 H 19 ClNO 3 S [M+H] + 364.0774, found 364.0766. 7-Bromo-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3g) White solid (38.4 mg, 94% yield). Mp = 90~91 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 8.8 Hz, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 7.07 (dd, J = 8.8, 2.0 Hz, 1H),7.04 (d, J = 2.0 Hz, 1H), 4.99 (s, 1H), 4.94 (s, 1H), 4.28 (dd, J = 14.8, 2.0 Hz, 1H), 3.50 (dd, J = 10.0, 2.0 Hz, 1H), 3.09 (dd, J = 14.8, 10.0 Hz, 1H), 2.41 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ148.0, 144.9, 140.1, 135.2, 130.3, 127.5, 126.3, 124.2, 122.8, 120.7, 119.1, 114.3, 74.3, 47.8, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 19 BrNO 3 S [M+H] + 408.0269, found 408.0277. 2-(Prop-1-en-2-yl)-4-tosyl-7-(trifluoromethyl)-3,4-dihydro-2H-benzo[b][1,4]oxazine (3h) Colerless oil (31.0 mg, 78% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.99 (d, J = 8.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.19 (dd, J = 8.8, 1.6 Hz, 1H), 7.16 (d, J = 1.6 Hz, 1H), 5.04-4.96 (m, 2H), 4.33 (dd, J = 14.8, 2.4 Hz, 1H), 3.62 (dd, J = 9.6, 2.4 Hz, 1H), 3.15 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H), 1.73 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.9, 145.1, 140.0, 135.3, 130.3, 128.2 (q, J = 32.9 Hz), 127.4, 126.7, 124.8, 123.9 (q, J = 270.0 Hz), 117.7 (q, J = 3.7 Hz), 115.2 (d, J = 3.9 Hz), 114.5, 74.8, 47.8, 21.8, 18.4. HRMS (ESI) calcd for C 19 H 19 F 3 NO 3 S [M+H] + 398.1038, found 398.1042. S15

6-Methyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3i) White solid (31.9 mg, 93% yield). Mp = 109~110 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.69 (d, J = 1.2 Hz,1H), 7.52 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 6.90 (dd, J = 8.4, 1.2 Hz, 1H), 6.76 (d, J = 8.4 Hz, 1H), 5.00-4.92 (m, 2H), 4.27 (dd, J = 14.4, 2.4 Hz, 1H), 3.51 (dd, J = 10.0, 2.0 Hz, 1H), 3.09 (dd, J = 14.4, 10.0 Hz, 1H), 2.39 (s, 3H), 2.33 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.1, 144.5, 140.7, 135.6, 130.5, 130.1, 127.5, 127.4, 125.2, 123.0, 117.3, 113.9, 74.0, 48.2, 21.8, 21.0, 18.4. HRMS (ESI) calcd for C 19 H 22 NO 3 S [M+H] + 344.1320, found 344.1318. 6-(tert-Butyl)-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3j) Colerless oil (37.4 mg, 97% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 2.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.11 (dd, J = 8.4, 2.4 Hz, 1H), 6.79 (d, J = 8.8 Hz, 1H), 5.00-4.95 (m, 2H), 4.31 (dd, J = 14.4, 2.4 Hz, 1H), 3.61 (dd, J = 10.0, 2.0 Hz, 1H), 3.13 (dd, J = 14.4, 10.0 Hz, 1H), 2.38 (s, 3H), 1.71 (s, 3H), 1.33 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.0, 144.5, 144.1, 140.9, 135.8, 130.1, 127.6, 123.5, 122.9, 122.0, 116.9, 114.0, 74.3, 48.3, 34.6, 31.7, 21.8, 18.5. HRMS (ESI) calcd for C 22 H 28 NO 3 S [M+H] + 386.1790, found 386.1774. 6-Nitro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3k) Yellow oil (31.4 mg, 84% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.79 (d, J = 2.8 Hz, 1H), 7.98 (dd, J = 9.2, 2.8 Hz, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 6.97 (d, J = 9.2 Hz, 1H), 5.08-4.98 (m, 2H), 4.35 (dd, J = 14.8, 2.4 Hz, 1H), 3.78 (dd, J = 10.0, 2.4 Hz, 1H), 3.18 (dd, J = 14.4, 10.0 Hz, 1H), 2.42 (s, 3H), 1.75 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 152.1, 145.3, 141.7, 139.5, S16

135.1, 130.4, 127.6, 123.8, 121.7, 120.5, 118.1, 115.0, 75.7, 47.3, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 19 N 2 O 5 S [M+H] + 375.1015, found 375.1029. 6-Fluoro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3l) White solid (32.3 mg, 93% yield). Mp = 112~113 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.72-7.50 (m, 3H), 7.28 (d, J = 7.6 Hz, 2H), 6.83-6.78 (m, 2H), 5.02-4.94 (m, 2H), 4.30 (dd, J = 14.4, 2.0 Hz, 1H), 3.53 (dd, J = 9.6, 2.0 Hz, 1H), 3.11 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H), 1.71 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.5 (d, J = 236.9 Hz), 144.7, 143.2, 140.2, 135.1, 130.1, 127.3, 123.7 (d, J = 10.9 Hz), 118.1 (d, J = 8.9 Hz), 114.0, 113.1 (d, J = 24.3 Hz), 111.0 (d, J = 27.6 Hz), 74.1, 47.8, 21.6, 18.3. HRMS (ESI) calcd for C 18 H 19 FNO 3 S [M+H] + 348.1070, found 348.1076. 6-Chloro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3m) White solid (33.5 mg, 92% yield). Mp = 112~113 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.92 (d, J = 2.4 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.8 Hz, 2H), 7.05 (dd, J = 8.8, 2.8 Hz, 1H), 6.80 (d, J = 8.8 Hz, 1H), 5.02-4.94 (m, 2H), 4.28 (dd, J = 14.4, 2.4 Hz, 1H), 3.52 (dd, J = 10.0, 2.0 Hz, 1H), 3.09 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H), 1.70 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.9, 145.0, 140.2, 135.2, 130.2, 127.5, 126.4, 125.8, 124.4, 124.3, 118.7, 114.3, 74.3, 47.8, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 19 ClNO 3 S [M+H] + 364.0774, found 364.0759. 6-Bromo-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3n) Colerless oil (29.4 mg, 72% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.05 (d, J = 2.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.18 (dd, J = 8.8, 2.4 Hz, 1H), 6.75 (d, J = 8.8 Hz, 1H), S17

5.01-4.94 (m, 1H), 4.28 (dd, J = 14.8, 2.4 Hz, 1H), 3.53 (d, J = 10.0, 1.6 Hz, 1H), 3.09 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H), 1.70 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.4, 145.0, 140.2, 135.2, 130.3, 129.3, 127.5, 127.3, 124.8, 119.2, 114.3, 112.9, 74.4, 47.8, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 19 BrNO 3 S [M+H] + 408.0269, found 408.0273. 2-(Prop-1-en-2-yl)-4-tosyl-6-(trifluoromethyl)-3,4-dihydro-2H-benzo[b][1,4]oxazine (3o) White solid (28.6 mg, 72% yield). Mp = 80~82 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d, J = 1.6 Hz, 1H), 7.54 (d, J = 8.4 Hz, 2H), 7.33 (dd, J = 8.4, 1.6 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 6.96 (d, J = 8.4 Hz, 1H), 5.04-4.96 (m, 2H), 4.32 (dd, J = 14.4, 2.4 Hz, 1H), 3.64 (dd, J = 10.0, 2.0 Hz, 1H), 3.13 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H), 1.72 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 149.6, 145.1, 140.0, 135.2, 130.3, 127.5, 124.2 (q, J = 269.9 Hz), 123.7, 123.4 (q, J = 32.9 Hz), 123.2 (q, J = 3.5 Hz), 122.4 (q, J = 3.9 Hz), 118.2, 114.5, 74.8, 47.6, 21.8, 18.4. HRMS (ESI) calcd for C 19 H 19 F 3 NO 3 S [M+H] + 398.1038, found 398.1012. 6,7-Dimethyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3p) White solid (35.0 mg, 98% yield). Mp = 55~57 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.63 (s, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.65 (s, 1H), 4.98-4.91(m, 2H), 4.24 (dd, J = 14.4, 2.4 Hz, 1H), 3.47 (dd, J = 10.4, 1.6 Hz, 1H), 3.07 (dd, J = 14.4, 10.0 Hz, 1H), 2.39 (s, 3H), 2.24 (s, 3H), 2.19 (s, 3H), 1.68 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.2, 144.4, 140.9, 135.7, 135.4, 130.1, 129.3, 127.5, 125.7, 120.7, 118.2, 113.8, 73.9, 48.3, 21.8, 19.6, 19.4, 18.4. HRMS (ESI) calcd for C 20 H 24 NO 3 S [M+H] + 358.1477, found 358.1489. 6,7-Dichloro-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3q) S18

White solid (13.5 mg, 34% yield). Mp = 86~88 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.02 (s, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 6.99 (s, 1H), 5.02-4.91 (m, 2H), 4.27 (dd, J = 14.4, 2.4 Hz, 1H), 3.49 (dd, J = 10.8, 2.0 Hz, 1H), 3.08 (dd, J = 14.4, 10.0 Hz, 1H), 2.42 (s, 3H), 1.69 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.2, 145.2, 139.8, 135.0, 130.4, 129.6, 127.5, 125.8, 124.3, 123.1, 119.1, 114.5, 74.5, 47.7, 21.8, 18.4. HRMS (ESI) calcd for C 18 H 18 Cl 2 NO 3 S [M+H] + 398.0384, found398.0368. 5-Methyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3r) Light yellow oil (6.9 mg, 20% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.56 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 7.09 (t, J = 8.0 Hz, 1H), 6.87 (d, J = 7.6 Hz, 1H), 6.70 (d, J = 8.0 Hz, 1H), 4.91-4.85 (m, 2H), 4.17-4.07 (m, 2H), 3.06 (dd, J = 15.2, 12.8 Hz, 1H), 2.51 (s, 3H), 2.42 (s, 3H), 1.61 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 150.8, 144.6, 141.5, 138.1, 136.4, 130.0, 128.1, 127.9, 123.7, 123.6, 114.7, 113.6, 75.9, 48.8, 21.8, 19.8, 17.7. HRMS (ESI) calcd for C 19 H 22 NO 3 S [M+H] + 344.1320, found 344.1325. 2-(Prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-naphtho[2,3-b][1,4]oxazine (3s) Colerless oil (32.3 mg, 85% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 8.36 (s, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.42-7.32 (m, 2H), 7.27 (s, 1H), 7.20 (d, J = 8.4 Hz, 2H), 5.06-5.01 (m, 2H), 4.41 (dd, J = 14.4, 2.4 Hz, 1H), 3.81 (dd, J = 10.0, 2.0 Hz, 1H), 3.31 (dd, J = 14.4, 10.4 Hz, 1H), 2.36 (s, 3H), 1.76 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.1, 144.7, S19

140.6, 136.0, 132.1, 130.2, 128.8, 128.1, 127.4, 126.3, 126.2, 124.6, 124.5, 122.2, 114.2, 112.8, 74.9, 48.3, 21.8, 18.5. HRMS (ESI) calcd for C 22 H 22 NO 3 S [M+H] + 380.1320, found380.1352. 4-Tosyl-2-vinyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3t) White solid (23.0 mg, 73% yield). Mp = 138~140 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (dd, J = 8.4, 1.2 Hz, 1H), 7.52 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.12-6.92 (m, 2H), 6.86 (dd, J = 8.0, 1.2 Hz, 1H), 5.74 (ddd, J = 17.2, 10.4, 6.0 Hz, 1H), 5.34-5.26 (m, 2H), 4.27 (dd, J = 14.4, 2.4 Hz, 1H), 3.79-3.72 (m, 1H), 3.15 (dd, J = 14.4, 10.0 Hz, 1H), 2.39 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.0, 144.6, 135.7, 133.4, 130.1, 127.4, 126.5, 124.8, 123.6, 121.2, 119.0, 117.7, 72.3, 48.5, 21.8. HRMS (ESI) calcd for C 17 H 18 NO 3 S [M+H] + 316.1007, found316.1015. 2-Methyl-2-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3u) White solid (30.9 mg, 90% yield). Mp = 98~100 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 8.4 Hz, 2H), 7.56 (dd, J = 8.4, 1.2 Hz, 1H), 7.28 (d, J = 8.4 Hz, 2H), 6.97-6.76 (m, 3H), 5.06-4.91 (m, 2H), 4.07 (d, J = 12.4 Hz, 1H), 3.64 (d, J = 12.4 Hz, 1H), 2.40 (s, 3H), 1.87 (s, 3H), 1.45 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 144.7, 144.4, 144.2, 136.8, 130.0, 127.2, 124.7, 124.5, 120.7, 118.8, 118.0, 113.4, 78.2, 51.3, 23.5, 21.7, 18.8. HRMS (ESI) calcd for C 19 H 22 NO 3 S [M+H] + 344.1320, found 344.1311. 2'-Methylene-4-tosyl-3,4-dihydrospiro[benzo[b][1,4]oxazine-2,1'-cyclohexane] (3v) White solid (25.1 mg, 68% yield). Mp = 119~121 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 6.99-6.77 (m, 3H), 4.89 (s, 1H), 4.82 (s, S20

1H), 4.05 (d, J = 13.2 Hz, 1H), 3.87 (d, J = 13.2 Hz, 1H), 2.42-2.26 (m, 5H), 1.95-1.45 (m, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.7, 145.1, 144.1, 137.3, 129.9, 127.2, 124.7, 124.6, 120.6, 119.2, 117.8, 110.5, 78.2, 49.9, 35.9, 33.4, 27.8, 23.0, 21.7. HRMS (ESI) calcd for C 21 H 24 NO 3 S [M+H] + 370.1477, found 370.1489. 2-(prop-1-enyl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3w) White solid (22.1 mg, 67% yield). Mp =152~154 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 7.6 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.07 (t, J = 8.0 Hz, 1H), 6.93 (t, J = 8.0 Hz, 1H), 6.82 (d, J = 8.0 Hz, 1H), 5.75-5.65 (m, 1H), 5.37 (dd, J = 15.2, 6.8 Hz, 1H), 4.22 (d, J = 14.0 Hz, 1H), 3.72-3.62 (m, 1H), 3.16-3.07 (m, 1H), 2.39 (s, 3H), 1.73 (d, J = 6.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.0, 144.3, 135.6, 131.5, 129.9, 127.3, 126.3, 126.3, 124.6, 123.4, 120.8, 117.5, 72.3, 48.6, 21.6, 17.9. HRMS (ESI) calcd for C 18 H 20 NO 3 S [M+H] + 330.1164, found 330.1178. 11-Tosyl-5a,8,9,10,10a,11-hexahydrobenzo[b]cyclohepta[e][1,4]oxazine (3x) White solid (23.1 mg, 65% yield). Mp = 117~119 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.94 (dd, J = 8.4, 1.2 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.07 (td, J = 8.0, 1.6 Hz, 1H), 6.96 (td, J = 8.0, 1.6 Hz, 1H), 6.85 (dd, J = 8.1, 1.2 Hz, 1H), 6.25-6.15 (m, 1H), 5.60 (dd, J = 11.6, 7.6 Hz, 1H), 4.36 (ddd, J = 11.6, 4.4, 2.0 Hz, 1H), 3.57-3.53 (m, 1H), 2.39 (s, 3H), 2.24-2.15 (m, 2H), 2.04-1.95 (m, 1H), 1.86-1.73 (m, 2H), 1.64-1.56 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.1, 144.3, 141.1, 135.6, 130.1, 127.3, 126.0, 125.5, 124.8, 122.3, 121.4, 117.5, 72.1, 55.3, 31.5, 28.2, 25.9, 21.8. HRMS (ESI) calcd for C 20 H 22 NO 3 S [M+H] + 356.1320, found 356.1331. (E)-2-Styryl-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (3y) S21

White solid (21.1 mg, 54% yield). Mp = 102~104 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (dd, J = 8.0, 1.6 Hz, 1H), 7.56 (d, J = 8.4 Hz, 2H), 7.39-7.24 (m, 7H), 7.15-7.06 (m, 1H), 7.00-6.93 (m, 1H), 6.89 (dd, J = 8.4, 1.6 Hz, 1H), 6.58 (d, J = 15.6 Hz, 1H), 6.06 (dd, J = 16.0, 6.4 Hz, 1H), 4.34 (dd, J = 14.4, 2.4 Hz, 1H), 4.00-3.94 (m, 1H), 3.25 (dd, J = 14.4, 10.0 Hz, 1H), 2.41 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.0, 144.6, 135.8, 135.7, 133.9, 130.2, 128.9, 128.6, 127.5, 126.9, 126.5, 124.8, 124.1, 123.6, 121.2, 117.7, 72.4, 48.8, 21.8. HRMS (ESI) calcd for C 23 H 22 NO 3 S [M+H] + 392.1320, found 392.1328. 10-Tosyl-2,4a,10,10a-tetrahydro-1H-phenoxazine (3z) White solid (11.3 mg, 33% yield). Mp = 126~128 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.89 (dd, J = 8.4, 1.6 Hz, 1H), 7.44 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.4 Hz, 2H), 7.11-6.91 (m, 2H), 6.78 (dd, J = 8.4, 1.2 Hz, 1H), 6.05-5.95 (m, 1H), 5.80-5.72 (m, 1H), 4.32 (dt, J = 13.2, 3.6 Hz, 1H), 3.53 (dd, J = 4.8, 3.6 Hz, 1H), 2.38 (s, 3H), 2.36-2.20 (m, 2H), 1.84-1.76 (m, 1H), 1.68-1.56 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.9, 144.3, 135.7, 134.1, 130.1, 127.3, 126.6, 125.9, 124.1, 121.4, 121.0, 117.2, 65.8, 52.3, 26.0, 22.8, 21.8. HRMS (ESI) calcd for C 19 H 20 NO 3 S [M+H] + 342.1164, found 342.1166. 3-(Prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4a) White solid (25.7 mg, 78% yield). Mp = 103~105 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 (dd, J = 8.0, 1.6 Hz, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.08-6.90 (m, 2H), 6.75 (dd, J = 8.0, 1.6 Hz, 1H), 5.02-4.91 (m, 2H), 4.71-4.67 (m, 1H), 4.29 (dd, J = 11.6, 1.6 Hz, 1H), 3.31 (dd, J = 11.6, 3.2 Hz, 1H), 2.39 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.7, 144.4, 139.4, 135.6, S22

130.1, 127.4, 126.4, 125.6, 122.6, 121.2, 117.2, 114.7, 63.4, 56.5, 21.8, 20.5. HRMS (ESI) calcd for C 18 H 20 NO 3 S [M+H] + 330.1164, found 330.1164. 7-Methyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4b) White solid (20.6 mg, 60% yield). Mp = 110~112 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 8.4 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.4 Hz, 2H), 6.75 (dd, J = 8.4, 2.0 Hz, 1H), 6.56 (d, J = 2.0 Hz, 1H), 5.05-4.88 (m, 2H), 4.67-4.61 (m, 1H), 4.26 (dd, J = 11.6, 1.6 Hz, 1H), 3.26 (dd, J = 11.6, 3.2 Hz, 1H), 2.39 (s, 3H), 2.26 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.4, 144.3, 139.5, 136.5, 135.7, 130.0, 127.5, 125.5, 122.2, 119.9, 117.5, 114.6, 63.3, 56.5, 21.8, 21.1, 20.5. HRMS (ESI) calcd for C 19 H 22 NO 3 S [M+H] + 344.1320, found 344.1314. 7-Ethyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4c) White solid (34.3 mg, 96% yield). Mp = 78~80 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 (d, J = 8.4 Hz, 1H), 7.50 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.78 (dd, J = 8.4, 2.0 Hz, 1H), 6.58 (d, J = 2.0 Hz, 1H), 5.03-4.91 (m, 2H), 4.67-4.62 (m, 1H), 4.26 (dd, J = 11.6, 1.6 Hz, 1H), 3.27 (dd, J = 11.6, 3.2 Hz, 1H), 2.56 (q, J = 7.6 Hz, 2H), 2.39 (s, 3H), 1.81 (s, 3H), 1.20 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.4, 144.3, 142.8, 139.5, 135.7, 130.0, 127.5, 125.4, 121.0, 120.0, 116.2, 114.6, 63.3, 56.6, 28.3, 21.8, 20.5, 15.2. HRMS (ESI) calcd for C 20 H 24 NO 3 S [M+H] + 358.1477, found 358.1443. 7-Methoxy-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4d) S23

White solid (34.1 mg, 95% yield). Mp = 106~108 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 9.2 Hz, 1H), 7.46 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.54 (dd, J = 9.2, 2.8 Hz, 1H), 6.28 (d, J = 2.8 Hz, 1H), 5.02-4.92 (m, 2H), 4.64-4.59 (m, 1H), 4.24 (dd, J = 11.6, 1.2 Hz, 1H), 3.75 (s, 3H), 3.24 (dd, J = 11.6, 3.2 Hz, 1H), 2.40 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 158.3, 147.7, 144.3, 139.6, 135.5, 130.1, 127.5, 127.1, 115.5, 114.6, 108.0, 101.7, 63.3, 56.3, 55.5, 21.8, 20.5. HRMS (ESI) calcd for C 19 H 22 NO 4 S [M+H] + 360.1270, found 360.1282. 7-Fluoro-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4e) White solid (32.7 mg, 94% yield). Mp = 100~102 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.83 (dd, J = 9.2, 6.0 Hz, 1H), 7.47 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.68 (ddd, J = 9.6, 8.0, 3.2 Hz, 1H), 6.48 (dd, J = 9.6, 2.8 Hz, 1H), 5.00-4.91 (m, 2H), 4.67-4.62 (m, 1H), 4.28 (dd, J = 11.2, 1.2 Hz, 1H), 3.26 (dd, J = 11.6, 3.2 Hz, 1H), 2.41 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.9 (d, J = 243.2 Hz), 147.7 (d, J = 12.3 Hz), 144.6, 139.2, 135.3, 130.2, 127.5, 127.2 (d, J = 9.7 Hz), 118.5 (d, J = 3.1 Hz), 114.8, 108.5 (d, J = 22.5 Hz), 104.3 (d, J = 25.6 Hz), 63.4, 56.1, 21.8, 20.5. HRMS (ESI) calcd for C 18 H 19 FNO 3 S[M+H] + 348.1070, found 348.1054. 7-Chloro-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4f) White solid (34.2 mg, 94% yield). Mp = 139~141 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.82 (d, J = 8.8 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 6.92 (dd, J = 9.2, 2.4 Hz, 1H), 6.77 (d, J = 2.4 Hz, 1H), 5.01-4.91 (m, 2H), 4.69-4.64 (m, 1H), 4.29 (dd, J = 11.6, 0.8 Hz, 1H), 3.25 (dd, J = 11.6, 3.2 Hz, 1H), 2.41 (s, 3H), 1.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.2, 144.7, 139.1, 135.3, 131.4, 130.2, 127.4, 126.6, 121.5, 121.2, 117.4, 114.9, 63.4, 56.3, 21.8, 20.4. HRMS (ESI) calcd for C 18 H 19 ClNO 3 S[M+H] + 364.0774, found 364.0786. S24

7-Bromo-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4g) White solid (38.8 mg, 95% yield). Mp = 81~83 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (d, J = 8.8 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4 Hz, 2H), 7.05 (dd, J = 8.8, 2.4 Hz, 1H), 6.92 (d, J = 2.4 Hz, 1H), 5.00-4.90 (m, 2H), 4.68-4.63 (m, 1H), 4.28 (dd, J = 11.6, 1.2 Hz, 1H), 3.24 (dd, J = 11.6, 3.6 Hz, 1H), 2.40 (s, 3H), 1.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 147.3, 144.7, 139.1, 135.3, 130.2, 127.4, 126.9, 124.4, 121.8, 120.3, 119.0, 114.9, 63.5, 56.3, 21.8, 20.4. HRMS (ESI) calcd for C 18 H 19 BrNO 3 S[M+H] + 408.0269, found 408.0287. 3-(Prop-1-en-2-yl)-4-tosyl-7-(trifluoromethyl)-3,4-dihydro-2H-benzo[b][1,4]oxazine (4h) White solid (37.4 mg, 94% yield). Mp = 114~116 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.00 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.4 Hz, 2H), 7.18 (dd, J = 8.4, 1.6 Hz, 1H), 7.03 (d, J = 2.0 Hz, 1H), 5.00-4.92 (m, 2H), 4.76-4.70 (m, 1H), 4.37 (dd, J = 11.6, 1.2 Hz, 1H), 3.32 (dd, J = 11.6, 3.2 Hz, 1H), 2.41 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.2, 144.9, 138.9, 135.2, 130.3, 128.0 (q, J = 32.9 Hz), 127.4, 125.8, 125.3, 123.8 (q, J = 270.3Hz), 117.9 (q, J = 3.7 Hz), 115.1, 114.7 (q, J = 3.9 Hz), 63.7, 56.5, 21.8, 20.4. HRMS (ESI) calcd for C 19 H 19 F 3 NO 3 S[M+H] + 398.1038, found 398.1046. 6-Methyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4i) White solid (28.2 mg, 82% yield). Mp = 128~130 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.69 (d, J = 1.2 Hz, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.86 (dd, J = 8.0, 1.6 Hz, 1H), 6.64 (d, J = 8.4 Hz, 1H), 5.03-4.91 (m, 2H), 4.67-4.63 (m, 1H), 4.25 (dd, J = 11.6, 1.6 Hz, 1H), 3.26 (dd, J = 11.6, 3.2 Hz, 1H), 2.39 (s, 3H), 2.32 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 144.4, 144.3, S25

139.5, 135.6, 130.6, 130.0, 127.5, 127.2, 125.8, 122.1, 116.8, 114.6, 63.3, 56.6, 21.8, 21.1, 20.5. HRMS (ESI) calcd for C 19 H 22 NO 3 S[M+H] + 344.1320, found 344.1312. 6-tert-Butyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4j) Colerless oil (37.4 mg, 97% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J = 2.4 Hz, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 7.05 (dd, J = 8.4, 2.4 Hz, 1H), 6.66 (d, J = 8.8 Hz, 1H), 5.04-4.91 (m, 2H), 4.76-4.70 (m, 1H), 4.28 (dd, J = 11.6, 1.6 Hz, 1H), 3.35 (dd, J = 11.6, 3.2 Hz, 1H), 2.38 (s, 3H), 1.83 (s, 3H), 1.32 (s, 9H). 13 C NMR (100 MHz, CDCl 3 ) δ 144.3, 144.2, 139.7, 135.8, 130.0, 127.5, 123.2, 122.2, 122.1, 116.4, 114.6, 63.6, 56.9, 34.5, 31.7, 21.8, 20.5. HRMS (ESI) calcd for C 22 H 28 NO 3 S[M+H] + 386.1790, found 386.1782. 6-Methoxy-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4k) White solid (26.6 mg, 74% yield). Mp = 67~69 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.55-7.46 (m, 3H), 7.24 (d, J = 8.4 Hz, 2H), 6.69-6.62 (m, 2H), 5.04-4.91 (m, 2H), 4.70-4.64 (m, 1H), 4.24 (dd, J = 11.6, 1.6 Hz, 1H), 3.80 (s, 3H), 3.25 (dd, J = 11.2, 3.2 Hz, 1H), 2.40 (s, 3H), 1.82 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 153.8, 144.4, 140.6, 139.5, 135.5, 130.1, 127.4, 122.8, 117.7, 114.6, 113.2, 109.5, 63.4, 56.9, 56.0, 21.8, 20.5. HRMS (ESI) calcd for C 19 H 22 NO 4 S[M+H] + 360.1270, found 360.1265. 6-Fluoro-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4l) White solid (33.0 mg, 95% yield). Mp = 130~132 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.69 (dd, J = 10.4, 2.8 Hz, 1H), 7.54 (d, J = 8.4 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 6.77 (ddd, J = 9.2, 7.6, 2.8 Hz, 1H), 6.70 (dd, J = 9.2, 5.6 Hz, 1H), 5.02-4.93 (m, 2H), 4.72-4.68 (m, 1H), 4.29 (dd, J = 11.2, 1.6 Hz, S26

1H), 3.26 (dd, J = 11.2, 3.2 Hz, 1H), 2.40 (s, 3H), 1.82 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.8 (d, J = 236.9 Hz), 144.7, 142.6 (d, J = 2.4 Hz), 139.2, 135.3, 130.2, 127.4, 123.1 (d, J = 10.9 Hz), 117.8 (d, J = 8.9 Hz), 114.8, 113.1 (d, J = 23.4 Hz), 111.7 (d, J = 27.5 Hz), 63.5, 56.6, 21.8, 20.4. HRMS (ESI) calcd for C 18 H 19 FNO 3 S[M+H] + 348.1070, found 348.1060. 6-Chloro-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4m) White solid (35.7 mg, 98% yield). Mp = 127~129 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.92 (d, J = 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.01 (dd, J = 8.8, 2.4 Hz, 1H), 6.69 (d, J = 8.8 Hz, 1H), 5.00-4.92 (m, 2H), 4.70-4.65 (m, 1H), 4.30 (dd, J = 11.6, 1.6 Hz, 1H), 3.26 (dd, J = 11.2, 3.2 Hz, 1H), 2.41 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.2, 144.8, 139.1, 135.3, 130.3, 127.5, 126.4, 125.9, 125.1, 123.4, 118.4, 115.0, 63.5, 56.4, 21.9, 20.5. HRMS (ESI) calcd for C 18 H 19 ClNO 3 S[M+H] + 364.0774, found 364.0776. 6-Bromo-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4n) White solid (29.0 mg, 71% yield). Mp = 150~152 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.05 (d, J = 2.4 Hz, 1H), 7.53 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.4 Hz, 2H), 7.15 (dd, J = 8.8, 2.4 Hz, 1H), 6.64 (d, J = 8.8 Hz, 1H), 5.00-4.92 (m, 2H), 4.69-4.65 (m, 1H), 4.30 (dd, J = 11.6, 1.6 Hz, 1H), 3.26 (dd, J = 11.6, 3.2 Hz, 1H), 2.41 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.7, 144.8, 139.0, 135.2, 130.2, 129.3, 127.9, 127.5, 123.8, 118.7, 114.9, 113.0, 63.5, 56.3, 21.8, 20.5. HRMS (ESI) calcd for C 18 H 19 BrNO 3 S[M+H] + 408.0269, found 408.0263. 3-(Prop-1-en-2-yl)-4-tosyl-6-(trifluoromethyl)-3,4-dihydro-2H-benzo[b][1,4]oxazine(4o) S27

White solid (29.0 mg, 73% yield). Mp = 75~77 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d, J = 1.2 Hz, 1H), 7.52 (d, J = 8.4 Hz, 2H), 7.30 (dd, J = 8.4, 2.4 Hz, 1H), 7.26 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.4 Hz, 1H), 4.99-4.93 (m, 2H), 4.75-4.71 (m, 1H), 4.38 (dd, J = 11.6, 1.2 Hz, 1H), 3.36 (dd, J = 11.6, 3.2 Hz, 1H), 2.41 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 149.0, 144.9, 138.9, 135.2, 130.3, 127.5, 126.8 (q, J = 246.1 Hz), 123.5 (q, J = 32.9 Hz), 123.2 (q, J = 3.7 Hz), 122.9 (q, J = 3.9 Hz), 122.6, 117.7, 115.0, 63.8, 56.1, 21.8, 20.4. HRMS (ESI) calcd for C 19 H 19 F 3 NO 3 S[M+H] + 398.1038, found398.1034. 6,7-Dimethyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4p) White solid (33.9 mg, 95% yield). Mp = 119~121 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.63 (s, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 6.53 (s, 1H), 5.04-4.91 (m, 2H), 4.63-4.58 (m, 1H), 4.22 (dd, J = 11.2, 1.6 Hz, 1H), 3.22 (dd, J = 11.6, 3.2 Hz, 1H), 2.39 (s, 3H), 2.22 (s, 3H), 2.16 (s, 3H), 1.81 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 144.4, 144.2, 139.6, 135.6, 135.2, 130.0, 129.4, 127.5, 126.3, 119.7, 117.8, 114.5, 63.2, 56.6, 21.8, 20.5, 19.6, 19.4. HRMS (ESI) calcd for C 20 H 24 NO 3 S[M+H] + 358.1477, found358.1484. 6,7-Dichloro-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4q) White solid (20.3 mg, 51% yield). Mp = 141~143 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.02 (s, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.28 (d, J = 8.4 Hz, 2H), 6.87 (s, 1H), 4.99-4.93 (m, 2H), 4.69-4.63 (m, 1H), 4.31 (dd, J = 11.6, 1.2 Hz, 1H), 3.23 (dd, J = 11.6, 3.2 Hz, 1H), 2.42 (s, 3H), 1.80 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.6, 145.0, 138.9, 135.1, 130.3, 130.1, 127.5, 126.3, 124.4, 122.2, 118.7, 115.1, 63.7, 56.2, 21.8, 20.4. HRMS (ESI) calcd for C 18 H 18 Cl 2 NO 3 S [M+H] + 398.0384, found 398.0410. 5-Methyl-3-(prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4r) S28

Colorless oil (11.4 mg, 33% yield). 1 H NMR (400 MHz, CDCl 3 ) δ 7.51 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 7.6 Hz, 2H), 7.05 (t, J = 7.8 Hz, 1H), 6.87 (dd, J = 7.6, 0.8 Hz, 1H), 6.59 (dd, J = 7.6, 1.2 Hz, 1H), 4.89-4.82 (m, 2H), 4.55-4.51 (m, 1H), 4.09 (dd, J = 11.6, 2.8 Hz, 1H), 3.83 (dd, J = 11.6, 6.0 Hz, 1H), 2.52 (s, 3H), 2.42 (s, 3H), 1.74 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 151.3, 144.4, 140.4, 138.9, 135.7, 129.9, 128.2, 127.6, 124.0, 122.0, 114.5, 114.2, 65.2, 57.9, 21.8, 20.3, 19.7. HRMS (ESI) calcd for C 19 H 22 NO 3 S[M+H] + 344.1320, found 344.1307. 3-(Prop-1-en-2-yl)-4-tosyl-3,4-dihydro-2H-naphtho[2,3-b][1,4]oxazine (4s) White solid (36.0 mg, 95% yield). Mp = 100~102 C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.37 (s, 1H), 7.81 (d, J = 7.6 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.52 (d, J = 7.6 Hz, 2H), 7.42-7.30 (m, 2H), 7.18 (d, J = 8.4 Hz, 2H), 7.15 (s, 1H), 5.09-4.93 (m, 2H), 4.87-4.82 (m, 1H), 4.35 (dd, J = 11.6, 1.6 Hz, 1H), 3.53 (dd, J = 11.6, 3.2 Hz, 1H), 2.36 (s, 3H), 1.85 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 145.4, 144.3, 139.5, 135.8, 131.9, 129.9, 128.8, 127.9, 127.2, 126.1, 126.0, 124.2, 123.7, 122.9, 114.9, 112.1, 64.0, 57.0, 21.6, 20.2. HRMS (ESI) calcd for C 22 H 22 NO 3 S[M+H] + 380.1320, found 380.1315. 4-Tosyl-3-vinyl-3,4-dihydro-2H-benzo[b][1,4]oxazine (4t) White solid (18.5 mg, 59% yield). Mp = 79~81 C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.89 (dd, J = 8.4, 1.6 Hz, 1H), 7.51 (d, J = 8.4 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.09-6.92 (m, 2H), 6.78 (dd, J = 8.0, 1.6 Hz, 1H), 5.73 (ddd, J = 17.2, 10.4, 4.4 Hz, 1H), 5.35 (ddd, J = 16.8, 1.6, 0.8 Hz, 1H), 5.21 (ddd, J = 10.4, 2.0, 0.8 Hz, 1H), 4.92-4.86 (m, 1H), 4.09 (dd, J = 11.2, 1.6 Hz, 1H), 3.34 (dd, J = 11.2, 2.8 Hz, 1H), 2.39 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 146.4, 144.4, 135.7, 132.8, 130.1, 127.4, 126.3, S29