# Natural Product-Oriented Photo-Induced Deintrogenative Annulations of 1-Alkenylbenzotriazoles
## 3 Materials and Methods
### General Procedure  
A quartz tube was charged with 1-alkenylbenzotriazoles (40 mg) at N\({}_{2}\) atmosphere. The freshly distilled THF or MeCN (5.0 mL) was added and the reaction mixture was stirred at room temperature for 3-10 h upon photolysis (254 nm). The resulting solution was concentrated in vacuo. The residue was directly purified by flash chromatography (silica gel, 200-300 mesh, hexanes/EtOAc or CH\({}_{2}\)Cl\({}_{2}\)/MeOH) to yield the corresponding product (Irradiation system, see Supplementary Materials). 2-(2-(1H-Benzo[d][1,2,3]triazole-1-yl)cyclohex-1-en-1-yl) ethanol (**15b**): colorless oil; Yield: 86%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.78-1.93 (m, 4H), 1.99 (t, \(J\) = 6.5 Hz, 2H), 2.33-2.39 (m, 2H), 2.41-2.47 (m, 2H), 2.53 (t, \(J\) = 5.3 Hz, 1H), 3.59-3.65 (m, 2H), 7.35 (ddd, \(J\) = 8.1, 5.9, 1.9 Hz, 1H), 7.42-7.51 (m, 2H), 8.02 (dd, \(J\) = 8.4, 1.0 Hz, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) \(\delta\) 145.6, 136.6, 132.9, 130.0, 127.8, 124.1, 120.1, 110.3, 60.0, 35.5, 29.6, 28.8, 22.9, 22.2. HRMS m/z calcd for C\({}_{14}\)H\({}_{18}\)N\({}_{3}\)O [M+H]\({}^{+}\): 244.1450; found: 244.1449. (4 bR,8 aR)-5,6,7,8-Tetrahydro-9H-8a,4b-(epoxyethano)carbazole (**17b**): white solid; Yield: 30%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.35-1.47 (m, 3H), 1.60-1.68 (m, 2H), 1.70-1.80 (m, 1H), 1.92-1.99 (m, 2H), 2.17-2.25 (m, 2H), 3.57-3.67 (m, 1H), 3.89-3.96 (m, 1H), 4.30 (s, 1H), 6.61 (m, 1H), 6.76 (t, \(J\) = 7.4 Hz, 1H), 7.02-7.08 (m, 2H).\({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 148.3, 135.6, 127.8, 122.8, 119.2, 109.2, 102.4, 66.2, 53.5, 38.0, 33.1, 32.4, 20.8, 19.7. HRMS m/z calcd for C\({}_{14}\)H\({}_{18}\)N\({}_{30}\) [M+H]\({}^{+}\): 216.1388; found: 216.1387. N-Phenylhexhexhydro-3 ad-cyclopent[2,3]cycloprop1,2-b]furan-3a-amine (**21**): white solid; Yield: ca. 30%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) 8 1.49-1.64 (m, 2H), 1.70-1.99 (m, 4H), 1.97-2.07 (m, 1H), 2.05-2.16 (m, 1H), 2.46 (q, \(J\) = 10.2 Hz, 1H), 3.53 (ddd, \(J\) = 10.1, 9.0, 7.7 Hz, 1H), 4.12 (td, \(J\) = 9.0, 2.2 Hz, 1H), 4.62 (s, 1H), 6.72-6.81 (m, 3H), 7.18 (td, \(J\) = 8.5, 7.2 Hz, 2H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) 8 145.8, 129.3, 118.7, 113.8, 79.4, 65.7, 39.8, 31.9, 30.8, 28.6, 26.3, 23.2. HRMS m/z calcd for C\({}_{14}\)H\({}_{18}\)N\({}_{30}\) [M+H]\({}^{+}\): 216.1388; found: 216.1387. 2-(2-(1H-Benzo[d][1,2,3]triazole-1-yl)-3,3-dimethylcyclohex-1-en-1-yl) ethanol (**15c**): colorless oil; Yield: 92%; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) \(\delta\) 0.89 (s, 3H), 1.15 (s, 3H), 1.50 (s, 1H), 1.56-1.74 (m, 2H), 1.75-1.83 (m, 2H), 1.83-1.94 (m, 2H), 2.26-2.46 (m, 2H), 3.50 (m, 2H), 7.36 (ddd, \(J\) = 8.1, 6.6, 1.4 Hz, 1H), 7.40-7.51 (m, 2H), 8.06 (dtd, \(J\) = 8.3, 1.1 Hz, 1H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) \(\delta\) 145.1, 138.2, 137.3, 134.8, 127.7, 123.9, 119.9, 110.9, 60.2, 39.2, 36.5, 35.8, 30.0, 28.5, 27.9, 19.0. HRMS m/z calcd for C\({}_{16}\)H\({}_{22}\)N\({}_{3}\)O [M+H]\({}^{+}\): 272.1763; found: 272.1761. (4 bR,8 aR)-8.8-Dimethyl-5,6,7,8-tetrahydro-9H-8a,4b-(epoxyethano)carbazole (**17c**): white solid; Yield: 56%; M.p. 106-107 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)) \(\delta\) 1.08 (s, 3H), 1.09 (s, 3H), 1.36-1.45 (m, 3H), 1.51-1.66 (m, 2H), 2.05-2.15 (m, 1H), 2.20-2.37 (m, 2H), 3.59 (ddd, \(J\) = 10.5, 8.1, 6.5 Hz, 1H), 3.91 (td, \(J\) = 8.1, 1.8 Hz, 1H), 4.41 (s, 1H), 6.63 (dt, \(J\) = 7.4, 1.0 Hz, 1H), 6.75 (td, \(J\) = 7.4, 1.0 Hz, 1H), 7.04 (t, \(J\) = 7.5 Hz, 2H). \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)) \(\delta\) 147.8, 136.9,127.7, 122.3, 119.0, 109.3, 105.9, 67.4, 54.3, 38.5, 37.4, 36.3, 33.6, 26.5, 25.2, 17.5. HRMS m/z calcd for C\({}_{16}\)H\({}_{22}\)NO [M+H]\({}^{+}\): 244.1701; found: 244.1702.