1H NMR (CDCl3, 400 MHz) d 7.44–7.35 (m, 5H), 4.77 (dd, J =
8.6, 4.2 Hz, 1H), 4.26 (dd, J = 8.4, 2.4 Hz, 2H), 3.80 (dd, J =
10.1, 4.2 Hz, 1H), 3.74 (dd, J = 10.1, 8.6 Hz, 1H), 2.48 (t, J =
2.4 Hz, 1H); 13C NMR (CDCl3, 125.8 MHz) d 136.4, 128.9, 128.8,
128.1, 127.1, 127.0, 79.1, 75.1, 73.5, 65.1, 58.6. HRMS (ESI, m/z)
calculated for C11H12N3O (MH+) 202.0980, found 202.0938.
1.70–1.40 (m, 4H); 13C NMR (CDCl3, 125.8 MHz) d 130.8, 128.3,
78.6, 62.3, 61.1, 30.4, 28.1, 24.0, 23.9. HRMS (ESI, m/z) calculated
for C9H14N3O (MH+) 180.1137, found 180.1133.
3-Methyl-4,5a,6,10b-tetrahydroindeno[2,1-b][1,2,3]triazolo[1,5-
d][1,4]oxazine (34). White solid; mp. 168–170 ◦C; 1H NMR
(CDCl3, 400 MHz) d 8.13 (d, J = 6.9 Hz, 1H), 7.39–7.34 (m,
3H), 5.22 (d, J = 14.7 Hz, 1H), 5.21 (d, J = 5.0 Hz, 1H), 5.05 (d,
J = 14.7 Hz, 1H), 4.08 (ddd, J = 11.0, 6.6, 5.0 Hz, 1H), 3.27 (dd,
J = 14.0, 6.6 Hz, 1H), 3.10 (dd, J = 14.0, 11.0 Hz, 1H), 2.31 (s,
3H); 13C NMR (CDCl3, 125.8 MHz) d 137.5, 135.1, 129.6, 128.7,
127.8, 127.2, 125.6, 125.2, 83.0, 64.2, 64.1, 33.6, 10.2. HRMS
(ESI, m/z) calculated for C13H14N3O (MH+) 228.1137, found
228.1125.
(S)-(1-Azido-2-(but-2-ynyloxy)ethyl)benzene
(4). Colorless
1
oil; [a]D 97.2 (c 1.4, CHCl3) IR (thin film) 2241, 2098 cm-1; H
NMR (CDCl3, 400 MHz) d 7.44–7.35 (m, 5H), 4.76 (dd, J = 8.8,
4.4 Hz, 1H), 4.27–4.19 (m, 2H), 3.77 (dd, J = 10, 8.8 Hz, 1H),
3.70 (dd, J = 10, 8.8 Hz, 1H), 1.87 (t, J = 2.4 Hz, 3H); 13C NMR
(CDCl3, 125.7 MHz) d 136.6, 129.0, 128.8, 128.6, 127.1, 127.0,
83.2, 74.5, 733, 65.2, 59.1, 3.7. HRMS (ESI, m/z) calculated for
C12H14N3O (MH+) 2216.1137, found 216.1124.
5a,6,7,11b-Tetrahydro-4H-naphtho[2,1-b][1,2,3]triazolo[1,5-d]-
[1,4]oxazine (35). As the precursor azidoalkyne 31 was found to
undergo partial cyclization during chromatographic purification,
it was subjected directly to the cycloaddition◦reaction step to afford
the product 35 as a white solid; mp. 121–122 C; 1H NMR (CDCl3,
400 MHz) d 8.54 (t, J = 3.4 Hz, 1H), 7.61 (s, 1H), 7.35–7.28
(m, 2H), 7.27–7.18 (m, 1H), 5.33 (d, J = 9.4 Hz, 1H), 5.18 (d,
J = 14.8 Hz, 1H), 4.93 (d, J = 14.8 Hz, 1H), 3.90 (m, 1H),
3.18–3.07 (m, 2H), 2.48–2.36 (m, 1H), 2.18–2.07 (m, 1H); 13C
NMR (CDCl3, 125.8 MHz) d 135.6, 132.3, 132.0, 128.5, 128.2,
128.1, 127.7, 126.5, 62.7 (2C), 61.5, 27.4, 26.2. HRMS (ESI, m/z)
calculated for C13H14N3O (MH+) 228.1137, found 228.1133.
(S)-7-Phenyl-6,7-dihydro-4H-[1,2,3]triazolo[5,1-c][1,4]oxazine
(5). White solid; mp. 90–91 ◦C; [a]D 67.9 (c 1.2, CHCl3); IR (thin
1
film) 2359, 2343 cm-1; H NMR (CDCl3, 400 MHz) d 7.62 (s,
1H), 7.42–7.35 (m, 3H), 7.17–7.14 (m, 2H), 5.66 (t, J = 5.0 Hz,
1H), 5.10 (d, J = 15.1 Hz, 1H), 5.04 (d, J = 15.1 Hz, 1H), 4.30
(dd, J = 12.1, 4.3 Hz, 1H), 4.08 (dd, J = 12.1, 5.6 Hz, 1H); 13C
NMR (CDCl3, 125.8 MHz) d 136.6, 131.3, 129.0, 128.9, 128.8,
128.1, 127.0 (2C), 70.6, 62.6, 59.8. HRMS (ESI, m/z) calculated
for C11H12N3O (MH+) 202.0980, found 202.0925.
(S)-3-Methyl-7-phenyl-6,7-dihydro-4H-[1,2,3]triazolo[5,1-c][1,
4]oxazine (6). White solid; mp. 101–103 ◦C; [a]D 77.1 (c 0.8,
CHCl3); 1H NMR (CDCl3, 400 MHz) d 7.33–7.31 (m, 3H), 7.13–
7.10 (m, 2H), 5.56 (t, J = 4.5 Hz, 1H), 4.96 (d, J = 14.8 Hz,
1H), 4.89 (d, J = 14.8 Hz, 1H), 4.20 (dd, J = 12.1, 4.3 Hz, 1H),
3.99 (dd, J = 12.1, 5.5 Hz, 1H), 2.31 (s, 3H); 13C NMR (CDCl3,
125.8 MHz) d 135.5, 135.4, 135.2, 134.5, 128.5, 127.6,127.4,127.2,
68.8, 61.2, 58.5, 8.0. HRMS (ESI, m/z) calculated for C12H14N3O
(MH+) 216.1137, found 216.1126.
5a,6,8,8a-Tetrahydro-4H-furo[3,4-b][1,2,3]triazolo[1,5-d][1,4]-
oxazine (47). Low melting solid; IR (thin film) 2359, 2341 cm-1;
1H NMR (CDCl3, 400 MHz) d 7.59 (s, 1H), 5.32 (d, J = 15.2 Hz.
1H), 5.11 (d, J = 15.2 Hz, 1H), 4.72 (dd, J = 8.0, 7.28 Hz, 1H), 4.43
(td, J = 9.6, 7.4 Hz, 1H), 4.22 (t, J = 7.3 Hz, 1H), 4.10 (m, 2H),
3.86 (dd, J = 10.0, 7.6 Hz, 1H); 13C NMR (CDCl3, 125.8 MHz)
d 130.7, 128.9, 79.6, 65.9, 65.6, 64.3, 60.0. HRMS (ESI, m/z)
calculated for C7H10N3O (MH+) 168.0733, found 168.0756.
(R)-6-Phenyl-6,7-dihydro-4H◦-[1,2,3]triazolo[5,1-c][1,4]oxazine
(9). White solid; mp. 136–137 C; 1H NMR (CDCl3, 400 MHz)
d 7.58 (s, 1H), 7.51–7.43 (m, 5H), 5.27 (d, J = 15.2 Hz, 1H), 5.03
(d, J = 15.2 Hz, 1H), 4.91 (dd, J = 10.6, 3.4 Hz, 1H), 4.76 (dd,
J = 13.1, 3.3 Hz, 1H), 4.33 (dd, J = 13.1, 10.6 Hz, 1H); 13C NMR
(CDCl3, 125.8 MHz) d 136.9, 130.4, 129.1, 129.0, 128.8, 128.2,
126.3, 126.1, 75.7, 62.3, 51.1. HRMS (ESI, m/z) calculated for
C11H12N3O (MH+) 202.0980, found 202.0980.
tert-Butyl 3-methyl-5a,6,8,8a-tetrahydropyrrolo[3,4-b][1,2,3]tri-
azolo[1,5-d][1,4]oxazine-7(4H)-carboxylate (50). White solid;
mp. 178–179 ◦C. 1H NMR (CDCl3, 400 MHz; rotameric mixture)
d 5.20 (d, J = 15.3 Hz, 1H), 5.00 (d, J = 15.3 Hz, 1H), 4.41 (dd,
J = 9.9, 7.5 Hz, 1H), 4.32–4.23 (m, 1H), 3.99–3.89 (m, 2H), 3.54
(t, J = 10.3 Hz, 1H), 3.40–3.35 (m, 1H), 2.30 (s, 3H), 1.52 (s,
9H); 13C NMR (CDCl3, 125.8 MHz; rotameric mixture) d 154.3,
137.9, 127.0, 80.7, 77.6, 63.8, 58.2, 45.6, 45.3, 28.4, 10.2. HRMS
(ESI, m/z) calculated for C13H21N4O3 (MH+) 281.1614, found
281.1602.
(R)-3-Methyl-6-phenyl-6,7-dihydro-4H-[1,2,3]triazolo[5,1-c][1,
4]oxazine (10). White solid; mp. 100–102 ◦C; 1H NMR (CDCl3,
400 MHz) d 7.33–7.31 (m, 3H), 7.13–7.10 (m, 2H), 5.56 (t, J =
4.5 Hz, 1H), 4.96 (d, J = 14.8 Hz, 1H), 4.89 (d, J = 14.8 Hz, 1H),
4.20 (dd, J = 12.1, 4.3 Hz, 1H), 3.99 (dd, J = 12.1, 5.5 Hz, 1H),
2.31 (s, 3H); 13C NMR (CDCl3, 125.8 MHz) d 135.5, 135.4, 135.2,
134.5, 128.5, 127.6, 127.4, 127.2, 68.8, 61.2, 58.5, 8.0. HRMS (ESI,
m/z) calculated for C12H14N3O (MH+) 216.1137, found 202.1126.
tert-Butyl 3-methyl-5a,6,7,8,9,9a-hexahydro-[1,2,3]triazolo[1,5-
a]quinoxaline-5(4H)-carboxylate (60). As the precursor azi-
doalkyne 59 was found to undergo partial cyclization during
chromatographic purification, it was subjected directly to the
cycloaddition reaction step to afford the product 60 as a white
◦
1
5a,6,7,8,9,9a-Hexahydro-4H -benzo[b][1,2,3]triazolo[1,5-d]-
[1,4]oxazine (21). As the precursor azidoalkyne 19 was found to
undergo partial cyclization during chromatographic purification,
it was subjected directly to the cycloaddition◦reaction step to afford
the product 21 as a white solid; mp. 102–104 C; 1H NMR (CDCl3,
400 MHz) d 7.50 (s, 1H), 5.11 (d, J = 15.0 Hz, 1H), 4.91 (d, J =
15.0 Hz, 1H), 4.02–3.94 (m, 1H), 3.45 (ddd, J = 11.0, 9.4, 4.0 Hz,
1H), 3.08–3.01 (m, 1H), 2.22–2.15 (m, 1H), 2.00–1.90 (m, 2H),
solid; mp. 166–167 C; H NMR (CDCl3, 500 MHz, rotameric
mixture) d 5.23 (br s, 1H), 4.37 (s, 1H), 4.17 (d, J = 13.2 Hz,
1H), 3.11 (d, J = 11.4 Hz, 1H), 2.22 (s, 3H), 1.81–1.70 (m, 1H),
1.69–1.55 (m, 2H), 1.53–1.47 (m, 1H), 1.45 (s, 9H), 1.40–1.01 (m,
4H); 13C NMR (CDCl3, 125.8 MHz, rotameric mixture) d 154.2,
138.2, 126.3, 81.2, 56.0, 52.2, 50.7, 37.2, 29.7, 28.4, 27.3, 24.6, 24.2,
19.1, 10.2. HRMS (ESI, m/z) calculated for C15H25N4O2 (MH+)
293.1977, found 293.1978.
This journal is
The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 1921–1930 | 1927
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