# Natural Product-Oriented Photo-Induced Deintrogenative Annulations of 1-Alkenylbenzotriazoles
## 3 Materials and Methods
### General Procedure
2-(6-(1H-Benzo[d][1,2,3]triazol-1-yl)spiro[4.5]dec-6-en-7-yl) ethanol (**15d**): colorless oil; Yield: 91%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 103-11.3 (m, 1H), 13-19 (m, 1H), 1.20-1.31 (m, 1H), 1.35-1.75 (m, 7H), 1.78-1.88 (m, 4H), 2.03-2.15 (m, 1H), 2.26-2.38 (m, 2H), 3.39-3.52 (m, 2H), 7.33 (ddd, \(J\) = 8.1, 6.6, 1.3 Hz, 1H), 7.38-7.49 (m, 2H), 7.97-8.04 (m, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 145.0, 138.9, 135.9, 135.1, 127.8, 123.9, 119.9, 110.7, 60.3, 47.5, 37.6, 36.5, 36.0, 36.0, 29.7, 24.2, 23.9, 19.7. HRMS m/z calcd for C\({}_{18}\)H\({}_{24}\)N\({}_{3}\)O [M+H]\({}^{+}\): 298.1919; found: 298.1921. (4b\({}^{\prime}\)R,8a\({}^{\prime}\)R)-6\({}^{\prime}\)7\({}^{\prime}\)-Dihydro-5\({}^{\prime}\)H,9\({}^{\prime}\)H-spiro(cyclopentane-18\({}^{\prime}\)-[8a,4b](epoxyethano)carbazole) (**17d**): white solid; Yield: 54%; M.p. 84-85 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 134-15.0 (m, 4H), 1.52-1.75 (m, 7H), 1.80-1.90 (m, 2H), 1.92-2.01 (m, 1H), 2.10-2.25 (m, 2H), 3.54 (ddd, \(J\) = 11.3, 8.3, 5.8 Hz, 1H), 3.91 (ddd, \(J\) = 8.7, 7.7, 1.3 Hz, 1H), 4.38 (s, 1H), 6.57 (dt, \(J\) = 7.6, 0.8 Hz, 1H), 6.72 (td, \(J\) = 7.4, 1.0 Hz, 1H), 6.99-7.06 (m, 2H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 148.9, 135.7, 127.8, 122.8, 118.6, 108.3, 106.2, 66.4, 54.7, 49.0, 39.7, 35.8, 34.3, 32.5, 32.2, 26.2, 25.0, 17.1. HRMS m/z calcd for C\({}_{18}\)H\({}_{24}\)NO [M+H]\({}^{+}\): 270.1858; found: 270.1857. 2-(2-(1H-Benzo[d][1,2,3]triazol-1-yl) cyclohex-1-en-1-yl) acetic acid (**15e**): white solid; Yield: 93%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.79-2.00 (m, 4H), 2.38-2.58 (m, 4H), 2.86 (s, 2H), 7.39 (m, 1H), 7.44-7.56 (m, 2H), 8.07 (d, \(J\) = 8.3 Hz, 1H), 11.34 (s, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 174.9, 145.2, 133.0, 132.3, 131.7, 128.1, 124.4, 119.9, 110.3, 37.8, 29.8, 29.4, 22.7, 22.0. HRMS m/z calcd for C\({}_{14}\)H\({}_{16}\)N\({}_{3}\)O\({}_{2}\) [M+H]\({}^{+}\): 258.1243; found: 258.1244. (4 bR,8 aR)-5,6,7,8-Tetrahydro-9h-8a,4b-(epoxyethano)carbazol-11-one (**17e**): yellow solid; Yield: 38%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.24-1.46 (m, 3H), 1.60-1.83 (m, 3H), 2.06-2.12 (m, 1H), 2.36-2.44 (m, 1H), 2.84-2.99 (m, 2H), 4.82 (s, 1H), 6.72 (dt, \(J\) = 7.8, 0.8 Hz, 1H), 6.85 (td, \(J\) = 7.5, 1.0 Hz, 1H), 7.06-7.16 (m, 2H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 174.1, 145.8, 134.9, 128.8, 123.1, 120.7, 110.4, 50.3, 38.4, 33.4, 33.0, 22.1, 20.2. HRMS m/z calcd for C\({}_{14}\)H\({}_{16}\)NO\({}_{2}\) [M+H]\({}^{+}\): 230.1181; found: 230.1183. 1-Methyl-2,3,4,9-tetrahydro-1H-carbazole (**22**): light yellow oil; Yield: 50%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.31 (d, \(J\) = 7.0 Hz, 3H), 1.49-1.58 (m, 1H), 1.71-1.85 (m, 1H), 1.96-2.09 (m, 2H), 2.66-2.78 (m, 2H), 2.93-3.05 (m, 1H), 7.04-7.16 (m, 2H), 7.27-7.33 (m, 1H), 7.44-7.50 (m, 1H), 7.76 (s, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 138.7, 135.8, 127.8, 121.2, 119.3, 118.1, 110.5, 109.9, 32.5, 28.8, 22.1, 21.3, 20.4. HRMS m/z calcd for C\({}_{13}\)H\({}_{16}\)N[M+H]\({}^{+}\): 186.1283; found: 186.1278. 2-(2-(1H-Benzo[d][1,2,3]triazol-1-yl)-3,3-dimethylcyclohex-1-en-1-yl)acetic acid (**15f**): white solid; Yield: 94%; M.p. 190-191 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 0.86 (s, 3H), 1.18 (s, 3H), 1.77-1.83 (m, 2H), 1.85-1.96 (m, 2H), 2.30 (dt, \(J\) = 17.9, 5.8 Hz, 1H), 2.40 (d, \(J\) = 16.7 Hz, 1H), 2.48 (dt, \(J\) = 18.1, 6.4 Hz, 1H), 2.58 (d, \(J\) = 16.7 Hz, 1H), 7.33 (ddd, \(J\) = 7.9, 6.5, 1.2 Hz, 1H), 7.38-7.47 (m, 2H), 8.04 (d, \(J\) = 8.2 Hz, 1H), 11.31 (s, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 175.4, 144.8, 138.9, 134.8, 134.1, 127.9, 124.2, 119.7, 111.1, 39.0, 37.7, 36.6, 30.4, 28.3, 27.6, 18.8. HRMS m/z calcd for C\({}_{16}\)H\({}_{20}\)N\({}_{3}\)O\({}_{2}\) [M+H]\({}^{+}\): 286.1556; found: 286.1556. (4 bR,8 aR)-8,8-Dimethyl-5,6,7,8-tetrahydro-9h-8a,4b-(epoxyethano)carbazol-11-one (**17f**): white solid; Yield: 63%; M.p.