1006
N.-C. Hsueh et al. / Tetrahedron 74 (2018) 1002e1008
4.2.4. 1-Azido-2-(4-trifluoromethylphenyl)propan-2-ol (4d)
Yield ¼ 75% (92 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C10H11F3N3O 246.0854, found 246.0859; 1H NMR
4.2.11. 5-Benzo[1,3]dioxol-5-yl-5,7,7-trimethyl-6,7-dihydro-5H-
indeno[5,6-d][1,3]dioxole (5a)
Yield ¼ 67% (54 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
(400 MHz, CDCl3):
3.61 (d, J ¼ 12.4 Hz, 1H), 3.49 (d, J ¼ 12.4 Hz, 1H), 2.43 (br s, 1H), 1.60
(s, 3H); 13C NMR (100 MHz, CDCl3):
d
7.64 (d, J ¼ 8.4 Hz, 2H), 7.58 (d, J ¼ 8.4 Hz, 2H),
H]þ calcd for C20H21O4 325.1440, found 325.1438; 1H NMR
(400 MHz, CDCl3):
d 6.71e6.62 (m, 4H), 6.53 (s, 1H), 5.96 (d,
d
148.62, 129.71 (q, J ¼ 32.6 Hz),
J ¼ 1.6 Hz, 1H), 5.95 (d, J ¼ 1.2 Hz, 1H), 5.91 (d, J ¼ 2.0 Hz, 1H), 5.91
(d, J ¼ 1.6 Hz, 1H), 2.34 (d, J ¼ 13.2 Hz, 1H), 2.16 (d, J ¼ 12.8 Hz, 1H),
1.61 (s, 3H), 1.29 (s, 3H), 1.05 (s, 3H); 13C NMR (100 MHz, CDCl3):
125.36 (4ꢂ), 121.34 (d, J ¼ 270.6 Hz), 74.42, 61.77, 27.08.
d
147.35, 147.19, 146.73, 145.33, 145.19 (2ꢂ), 141.49, 119.42, 107.63,
4.2.5. 1-Azido-2-biphenyl-4-ylpropan-2-ol (4e)
107.41, 104.90, 102.79, 101.01, 100.77, 59.68, 50.33, 42.56, 30.93,
30.87, 30.37.
Yield ¼ 73% (92 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C15H16N3O 254.1293, found 254.1299; 1H NMR
(400 MHz, CDCl3):
d
7.63e7.58 (m, 4H), 7.53 (d, J ¼ 8.4 Hz, 2H),
7.47e7.43 (m, 2H), 7.38e7.34 (m, 1H), 3.66 (d, J ¼ 12.4 Hz, 1H), 3.50
4.2.12. 4,5,6-Trimethoxy-1,1,3-trimethyl-3-(3,4,5-
trimethoxyphenyl)indan (5b)
(d, J ¼ 12.4 Hz, 1H), 2.20 (br s, 1H), 1.64 (s, 3H); 13C NMR (100 MHz,
CDCl3):
d
143.66, 140.56, 140.43, 128.78 (2ꢂ), 127.38, 127.19 (2ꢂ),
Yield ¼ 63% (66 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C24H33O6 417.2277, found 417.2273; 1H NMR
127.08 (2ꢂ), 125.33 (2ꢂ), 74.51, 62.10, 27.18.
(400 MHz, CDCl3):
d 6.43 (s, 1H), 6.37 (s, 2H), 3.85 (s, 3H), 3.78 (s,
3H), 3.76 (s, 3H), 3.72 (s, 6H), 3.57 (s, 3H), 2.29 (d, J ¼ 12.8 Hz, 1H),
4.2.6. 1-Azido-2-(3,4-dichlorophenyl)propan-2-ol (4f)
2.09 (d, J ¼ 13.2 Hz, 1H), 1.73 (s, 3H), 1.27 (s, 3H), 1.05 (s, 3H); 13C
Yield ¼ 70% (86 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
NMR (100 MHz, CDCl3):
d
153.68, 152.21 (2ꢂ), 149.99, 147.48,
H]þ calcd for C9H10Cl3N3O 246.0201, found 246.0208; 1H NMR
146.73, 140.81, 135.52, 132.56, 130.75 (2ꢂ), 100.66, 60.52, 60.25,
(400 MHz, CDCl3):
d
7.56 (d, J ¼ 2.4 Hz, 1H), 7.43 (d, J ¼ 8.4 Hz, 1H),
59.97, 59.82, 55.84, 55.76, 55.74, 50.79, 43.19, 30.81, 30.34, 28.91.
7.25 (dd, J ¼ 2.4, 8.4 Hz, 1H), 3.55 (d, J ¼ 12.4 Hz, 1H), 3.44 (d,
J ¼ 12.4 Hz, 1H), 2.41 (br s, 1H), 1.56 (s, 3H); 13C NMR (100 MHz,
CDCl3):
27.00.
d 144.94, 132.60, 131.52, 130.33, 127.31, 124.40, 73.97, 61.65,
4.2.13. 1-Azido-2-phenylethan-2-ol (4n)
Yield ¼ 56% (46 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C8H10N3O 164.0824, found 164.0823; 1H NMR
(400 MHz, CDCl3):
d
7.40e7.32 (m, 5H), 4.88 (dd, J ¼ 3.6, 8.0 Hz, 1H),
4.2.7. 1-Azido-2-(3-fluorophenyl)propan-2-ol (4g)
3.48 (dd, J ¼ 8.0, 12.4 Hz, 1H), 3.42 (dd, J ¼ 3.6, 12.4 Hz, 1H), 2.60 (br
Yield ¼ 81% (79 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
s, 1H); 13C NMR (100 MHz, CDCl3):
d
140.66, 128.75 (2ꢂ), 128.34,
H]þ calcd for C9H11FN3O 196.0886, found 196.0892; 1H NMR
125.92 (2ꢂ), 73.25, 58.11.
(400 MHz, CDCl3):
(m, 1H), 3.55 (d, J ¼ 12.4 Hz, 1H), 3.41 (d, J ¼ 12.4 Hz, 1H), 2.41 (br s,
1H), 1.54 (s, 3H); 13C NMR (100 MHz, CDCl3):
162.91 (d,
d 7.33e7.27 (m,1H), 7.18e7.14 (m, 2H), 6.98e6.93
d
4.3. A representative synthetic procedure of compounds 6a-6e is as
follows
J ¼ 244.0 Hz), 147.42 (d, J ¼ 6.8 Hz), 129.98 (d, J ¼ 8.3 Hz), 120.44 (d,
J ¼ 3.0 Hz), 114.33 (d, J ¼ 21.2 Hz), 112.32 (d, J ¼ 22.8 Hz), 74.28 (d,
J ¼ 1.5 Hz), 61.85, 27.05.
BiI3 (3a, 354 mg, 0.6 mmol) was added to a stirred solution of
1a-1b, 1d, 1f and 1h (0.5 mmol) in dry DMF (5 mL) at 25 ꢁC. The
reaction mixture was stirred at 25 ꢁC for 15 min NaN3 (2a, 39 mg,
0.6 mmol) was added to the reaction mixture at 25 ꢁC. Then, the
reaction mixture was stirred at reflux for 2 h. The reaction mixture
was cooled to 25 ꢁC and the solvent was concentrated. The residue
was diluted with water (10 mL) and the mixture was extracted with
CH2Cl2 (3 ꢂ 20 mL). The combined organic layers were washed with
brine, dried, filtered and evaporated to afford crude product under
reduced pressure. Purification on silica gel (hexanes/EtOAc ¼ 8/
1e4/1) afforded 6a-6e.
4.2.8. 1-Azido-2-pyridin-4-ylpropan-2-ol (4h)
Yield ¼ 70% (62 mg); Colorless solid; mp ¼ 103e105 ꢁC (recrys-
tallized from hexanes and EtOAc); HRMS (ESI-TOF) m/z: [M þ H]þ
calcd for C8H11N4O 179.0933, found 179.0938; 1H NMR (400 MHz,
CDCl3):
d
8.42 (d, J ¼ 6.4 Hz, 2H), 7.39 (d, J ¼ 6.4 Hz, 2H), 5.15 (br s,
1H), 3.47 (d, J ¼ 12.4 Hz, 1H), 3.40 (d, J ¼ 12.4 Hz, 1H), 1.54 (s, 3H);
13C NMR (100 MHz, CDCl3):
73.60, 61.18, 26.48.
d
155.16, 148.83 (2ꢂ), 120.51 (2ꢂ),
4.2.9. 1-Azido-2-naphthalen-2-yl-propan-2-ol (4i)
4.3.1. (2-Azido-1-iodo-1-methylethyl)benzene (6a)
Yield ¼ 72% (82 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C13H14N3O 228.1137, found 228.1135; 1H NMR
Yield ¼ 76% (109 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H11IN3 287.9998, found 287.9990; 1H NMR
(400 MHz, CDCl3):
d
7.95 (d, J ¼ 2.0 Hz, 1H), 7.86 (d, J ¼ 8.8 Hz, 2H),
(400 MHz, CDCl3):
d 7.46e7.39 (m, 4H), 7.36e7.32 (m, 1H), 3.51 (d,
7.86e7.83 (m, 1H), 7.54e7.47 (m, 3H), 3.72 (d, J ¼ 12.4 Hz, 1H), 3.56
J ¼ 14.4 Hz, 1H), 3.48 (d, J ¼ 14.4 Hz, 1H), 1.89 (s, 3H); 13C NMR
(d, J ¼ 12.4 Hz, 1H), 2.41 (br s, 1H), 1.69 (s, 3H); 13C NMR (100 MHz,
(100 MHz, CDCl3):
25.16, 17.68.
d
140.73, 128.79 (2ꢂ), 128.27, 125.60 (2ꢂ), 65.07,
CDCl3):
d 141.99, 133.14, 132.60, 128.26, 128.19, 127.54, 126.32,
126.14, 123.76, 122.99, 74.74, 62.01, 27.18.
4.2.10. 2-Azido-1-methyl-1,2,3,4-tetrahydronaphthalen-1-ol (4j)
Yield ¼ 43% (44 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C11H14N3O 204.1137, found 204.1133; 1H NMR
4.3.2. 1-(2-Azido-1-iodo-1-methylethyl)-4-fluorobenzene (6b)
Yield ¼ 68% (104 mg); Colorless oil; HRMS (ESI-TOF) m/z: [M þ
H]þ calcd for C9H10FIN3 305.9904, found 305.9910; 1H NMR
(400 MHz, CDCl3):
(d, J ¼ 8.0 Hz, 1H), 3.74 (dd, J ¼ 3.6, 12.0 Hz, 1H), 2.96e2.92 (m, 2H),
2.40 (br s,1H), 2.20e2.13 (m,1H),1.96e1.85 (m,1H),1.49 (s, 3H); 13
NMR (100 MHz, CDCl3): 141.68, 133.79, 128.24, 27.43, 126.64,
126.10, 74.26, 67.67, 27.51, 25.83, 25.26.
d
7.59 (d, J ¼ 8.8 Hz, 1H), 7.27e7.19 (m, 2H), 7.08
(400 MHz, CDCl3): d 7.44e7.39 (m, 2H), 7.11e7.05 (m, 2H), 3.49 (d,
J ¼ 10.4 Hz, 1H), 3.45 (d, J ¼ 10.4 Hz, 1H), 1.88 (s, 3H); 13C NMR
C
(100 MHz, CDCl3):
127.47 (d, J ¼ 8.3 Hz, 2ꢂ), 115.55 (d, J ¼ 21.2 Hz, 2ꢂ), 64.55, 25.07,
d
162.26 (d, J ¼ 247.2 Hz), 136.56 (d, J ¼ 3.8 Hz),
d
17.43.