C29H28N4O3Na+: 503.2054; Found: 503.2049; HPLC (254 nm,
Method 2): 8.533 min, 96.7%.
9-(Trityloxymethyl)-4,5,9a,10-tetrahydrooxazolo[3,4-α]-[1,2,3]
triazolo[1,5-d][1,4]-diazepin-7(9H)-one (7i). Prepared by
Method A using 87 mg (0.19 mmol) of 6i which provided
82 mg (95%) of 7i as a white solid; mp 219.3–220.7 °C; Rf =
3-Phenyl-10-(trityloxymethyl)-5,6,10a,11-tetrahydro-4H-oxazolo-
1
0.20 (hexanes–EtOAc, 1 : 3); IR (KBr): 1755 cm−1; H NMR
[3,4-a][1,2,3]triazo-lo[1,5-d][1,4]diazocin-8(10H)-one
(7m). Pre-
pared by Method B using 64 mg (0.12 mmol) of 6m which pro-
vided 57 mg of 7m (89%) as a pale yellow solid; mp
92.9–94.4 °C; Rf = 0.51 (hexanes–EtOAc, 2 : 3); IR (KBr):
(300 MHz, CDCl3): δ 7.51 (br s, 1H), 7.42–7.39 (m, 6H),
7.34–7.22 (m, 9H), 4.86 (dd, J = 14.1, 1.6 Hz, 1H), 4.34–4.18
(m, 3H), 3.61 (AB dd, JAB = 10.7 Hz, δA = 3.63, J = 5.4, 1.8
Hz, δB = 3.59, J = 5.4, 1.8 Hz, 1H), 3.40 (AB dd, JAB = 32.6
Hz, δA = 3.46, J = 10.6, 4.7 Hz, δB = 3.35, J = 10.6, 4.1 Hz,
2H), 3.21–3.14 (m, 1H), 2.95–2.80 (m, 2H); 13C NMR
(75 MHz, CDCl3): δ 156.3, 143.1, 136.4, 133.6, 128.5, 128.2,
127.5, 87.4, 74.7, 63.6, 58.0, 54.6, 42.5, 24.4; HRMS-ESI: m/z
[M + Na]+ calcd for C28H26N4O3Na+: 489.1897; Found:
489.1897; HPLC (214 nm, Method 1): 12.567 min, 92.3%.
1
1755 cm−1; H NMR (300 MHz, CDCl3): δ 7.73–7.64 (m, 2H),
7.51–7.38 (m, 8H), 7.38–7.19 (m, 10H), 4.64–4.33 (m, 3H),
3.98 (dd, J = 12.9, 1.8 Hz, 1H), 3.84 (dd, J = 9.0, 5.6 Hz, 1H),
3.41 (ddd, J = 14.2, 10.4, 4.3 Hz, 2H), 3.13–3.05 (m, 1H),
2.87–2.83 (m, 1H), 2.65 (t, J = 13.2 Hz, 1H), 2.43–2.21 (m,
1H), 1.99–1.92 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 156.9,
145.0, 143.1, 133.2, 131, 128.9, 128.5, 128.1, 127.4, 127.1,
87.3, 74.5, 63.4, 60.9, 50.3, 43.7, 28.2, 20.9; HRMS-ESI: m/z
[M + Na+] calcd for C35H32N4O3Na+: 579.2367; Found:
579.2362; HPLC (254 nm, Method 2): 12.933 min, 94.7%.
3-Methyl-9-(trityloxymethyl)-4,5,9a,10-tetrahydrooxazolo [3,4-
α][1,2,3]triazolo[1,5-d][1,4]diazepin-7(9H)-one (7j). Prepared by
Method A using 145 mg (0.30 mmol) of 6j which provided
143 mg (99%) of 7j as a white solid; mp 101.8–102.7 °C; Rf =
11-(Trityloxymethyl)-4,5,6,7,11a,12-hexahydrooxazolo[3,4-a]-
[1,2,3]triazolo[1,5-d]-[1,4]diazonin-9(11H)-one (7n). Prepared
by Method B using 61 mg (0.12 mmol) of 6n which provided
49 mg (80%) of 7n as a white solid; mp 73.1–74.5 °C; Rf = 0.18
1
0.16 (hexanes–EtOAc, 1 : 4); IR (KBr): 1755 cm−1; H NMR
(300 MHz, CDCl3): δ 7.38–7.24 (m, 15H), 4.78 (dd, J = 14.2,
1.8 Hz, 1H), 4.34–4.29 (m, 1H), 4.24–4.15 (m, 2H), 3.65 (AB
dd, JAB = 10.7 Hz, δA = 3.67, J = 5.4, 1.8 Hz, δB = 3.63, J =
5.4, 1.8 Hz, 1H), 3.40 (AB dd, JAB = 54.2 Hz, δA = 3.49, J =
10.6, 4.5 Hz, δB = 3.31, J = 10.6, 4.1 Hz, 2H), 3.08–3.02 (m,
1H), 2.93–2.74 (m, 2H), 2.29 (s, 3H); 13C NMR (75 MHz,
CDCl3): δ 156.4, 143.1, 141.6, 132.8, 128.5, 128.1, 127.5, 87.4,
74.8, 63.6, 58.0, 54.7, 42.5, 23.8, 10.1; HRMS-ESI: m/z [M +
Na]+ calcd for C29H28N4O3Na+: 503.2054; Found: 503.2056;
HPLC (214 nm, Method 1): 12.925 min, 92.5%.
(hexanes–EtOAc, 1 : 2); IR (KBr): 1754 cm−1
;
1H NMR
(300 MHz, CDCl3): δ 7.47–7.39 (m, 6H), 7.37–7.21 (m, 9H),
4.59 (dd, J = 14.5, 2.4 Hz, 1H), 4.45 (dd, J = 9.2, 4.4 Hz, 1H),
4.37 (dd, J = 14.5, 8.0 Hz, 1H), 3.86 (ddd, J = 8.0, 5.6, 2.4 Hz,
1H), 3.67–3.57 (m, 1H), 3.50 (dd, J = 10.4, 4.6 Hz, 1H), 3.30
(dd, J = 10.4, 3.9 Hz, 1H), 3.00–2.71 (m, 2H), 2.22–2.04 (m,
2H), 1.94 (dd, J = 11.2, 5.6 Hz, 2H), 1.47–1.30 (m, 1H); 13C
NMR (75 MHz, CDCl3): δ 157.8, 143.1, 138.0, 133.6, 128.6,
128.1, 127.4, 87.3, 75.2, 63.9, 60.7, 51.5, 43.6, 25.6, 23.4, 22.0;
HRMS-ESI: m/z [M
+
Na+] calcd for C30H30N4O3Na+:
3-Phenyl-9-(trityloxymethyl)-4,5,9a,10-tetrahydrooxazolo-[3,4-
α][1,2,3]triazolo[1,5-d][1,4]diazepin-7(9H)-one (7k). Prepared by
Method A using 91 mg (0.17 mmol) of 6k which provided
85 mg (93%) of 7k as a white solid; mp 103.9–105.2 °C; Rf =
517.2210; Found: 517.2205; HPLC (254 nm, Method 3):
12.842 min, 97.2%.
12-(Trityloxymethyl)-5,6,7,8,12a,13-hexahydro-4H-oxazolo [3,4-
a][1,2,3]triazolo[1,5-d][1,4]diazecin-10(12H)-one (7o). Prepared
by Method B using 61 mg (0.12 mmol) of 6o which provided
46 mg (76%) of 7o as a white solid; mp 92.5–93.8 °C; Rf = 0.38
1
0.10 (hexanes–EtOAc, 3 : 2); IR (KBr): 1759 cm−1; H NMR
(300 MHz, CDCl3): δ 7.57–7.54 (m, 2H), 7.47–7.37 (m, 9H),
7.31–7.22 (m, 9H), 4.84 (dd, J = 14.2, 1.5 Hz, 1H), 4.31–4.21
(m, 3H), 3.69 (ddd, J = 10.5, 5.4, 1.5 Hz, 1H), 3.48 (dd, J =
10.5, 4.6 Hz, 1H), 3.39–3.32 (m, 2H), 2.93–2.88 (m, 2H); 13C
NMR (75 MHz, CDCl3): δ 156.2, 145.9, 143.1, 133, 130.7,
128.9, 128.5, 128.3, 128.1, 127.9, 127.4, 87.3, 74.6, 63.6, 57.8,
54.8, 42.3, 24.2; HRMS-ESI: m/z [M + Na]+ calcd for
C34H30N4O3Na+: 565.2210; Found: 565.2212; HPLC (214 nm,
Method 2): 14.417 min, 100.0%.
(hexanes–EtOAc, 1 : 8); IR (KBr): 1756 cm−1
;
1H NMR
(300 MHz, CDCl3): δ 7.45–7.42 (m, 7H), 7.34–7.22 (m, 9H),
5.19 (br s, 1H), 4.41 (dd, J = 15.1, 3.1 Hz, 1H), 4.28 (dd, J =
15.1, 3.5 Hz, 1H), 3.91 (d, J = 3.5 Hz, 1H), 3.76–3.66 (m, 1H),
3.56 (dd, J = 10.4, 4.1 Hz, 1H), 3.21 (dd, J = 10.4, 3.0 Hz, 1H),
2.90–2.63 (m, 3H), 1.84–1.52 (m, 4H), 1.26–1.19 (m, 2H); 13C
NMR (75 MHz, CDCl3): δ 159.2, 143.2, 138.5, 132.4, 128.6,
128.1, 127.3, 87.1, 75.3, 63.8, 60.6, 49.1, 45.8, 27.4, 24.7, 20.8;
+
Na+] calcd for C31H32N4O3Na+:
10-(Trityloxymethyl)-5,6,10a,11-tetrahydro-4H-oxazolo[3,4-α]-
[1,2,3]triazolo[1,5-d]-[1,4]diazocin-8(10H)-one (7l). Prepared by
Method A using 32 mg (0.067 mmol) of 6l which provided
31 mg (98%) of 7l as a white solid; mp 95.9–97.4 °C; Rf = 0.15
HRMS-ESI: m/z [M
531.2367; Found: 531.2369; HPLC (254 nm, Method 2):
11.417 min, 99.7%.
(hexanes–EtOAc, 1 : 2); IR (KBr): 1756 cm−1
;
1H NMR
13-(Trityloxymethyl)-4,5,6,7,8,9,13a,14-octahydrooxazolo-[3,4-
a][1,2,3]triazolo[1,5-d][1,4]diazacycloundecin-11(13H)-one (7p).
Prepared by Method B using 92 mg (0.18 mmol) of 6p which
provided 48 mg (52%) of 7p as a white solid; mp 77.5–79.4 °C;
(300 MHz, CDCl3): δ 7.51–7.37 (m, 7H), 7.37–7.17 (m, 9H),
4.54–4.34 (m, 3H), 3.91 (ddd, J = 14.7, 3.6, 2.4 Hz, 1H), 3.80
(dd, J = 9.9, 4.3 Hz, 1H), 3.38 (ddd, J = 14.2, 10.4, 4.3 Hz, 2H),
3.09–2.91 (m, 1H), 2.78–2.47 (m, 2H), 2.27–2.09 (m, 1H),
1.89–1.78 (m, 1H); 13C NMR (75 MHz, CDCl3): δ 156.8, 143.1,
137.3, 132.9, 128.5, 128.1, 127.4, 87.2, 74.5, 63.4, 60.8, 49.3,
43.6, 28.7, 20.7; HRMS-ESI: m/z [M + Na+] calcd for
Rf = 0.52 (hexanes–EtOAc, 1 : 4); IR (KBr): 1756 cm−1 1H
;
NMR (300 MHz, CDCl3): δ 7.51–7.41 (m, 7H), 7.38–7.21 (m,
9H), 4.60 (t, J = 6.7 Hz, 1H), 4.40–4.23 (m, 3H), 3.55 (dd, J =
10.4, 4.6 Hz, 1H), 3.44–3.31 (m, 2H), 2.84–2.77 (m, 2H),
3088 | Org. Biomol. Chem., 2012, 10, 3080–3091
This journal is © The Royal Society of Chemistry 2012