1
0
Tetrahedron
13
3
H), 0.80 (s, 6H), 0.76 (s, 3H), 0.75 (s, 3H); C NMR (101
134.5, 129.9, 128.8, 127.9, 123.6, 119.9, 109.5, 81.4, 55.6, 55.4,
50.4, 50.0, 49.8, 46.8, 42.4, 40.7, 39.5, 38.3, 38.1, 37.8, 37.7,
37.0, 34.3, 34.2, 33.3, 30.8, 29.6, 29.3, 27.8, 25.5, 23.6, 20.9,
19.4, 18.1, 16.5, 16.2, 15.7, 14.6; ESIMS: m/z 810.75 [100%,
ACCEPTED MANUSCRIPT
MHz, CDCl ): δ (ppm) 176.5, 176.3, 172.6, 150.8, 145.4, 135.1,
3
1
5
3
2
33.8, 129.8, 129.7, 128.9, 128.7, 113.9, 109.5, 80.9, 55.6, 55.4,
0.4, 50.1, 48.6, 46.8, 43.8, 42.4, 40.7, 38.3, 38.2, 37.8, 37.7,
7.0, 34.6, 34.2, 33.4, 30.8, 30.1, 30.0, 29.7, 29.4, 27.9, 25.5,
+
+
(M+H) ], HRMS-ESI: calculated for C H N O [M+H]
832.4984, found 832.5026.
48
67
5
6
3.6, 20.9, 19.4, 18.1, 16.5, 16.2, 15.8, 14.6; ESIMS: m/z
+
calculated for C H N O (M+H) 881.59, found 881.58.
52
76
6
6
Preparation of N-Propargyl pyrazinylbetulinamide 23: The
title compound was prepared by the reaction of compound 22
(450 mg, 0.9 mmol) and propargyl amine (60 mg, 1.1 mmol) as
per the general amide-coupling procedure A to yield 387 mg
Preparation of succinic acid hemiester 21c: Procedure similar
to that of 21a. Yield: 83%; cream color solid; mp 142 – 145 °C;
1
H NMR (400 MHz, CDCl ): δ (ppm) 7.61 (s, 1H), 7.36 – 7.44
3
1
(m, 5H), 6.88 (s, 1H), 6.58 (t, J = 5.7 Hz, 1H), 5.34 (s, 2H), 4.72
(80%) of 23 as a white solid. Mp 122 – 125 °C; H NMR (400
(s, 1H), 4.58 (s, 1H), 4.43 – 4.50 (m, 3H), 3.73 (brs, 4H) 3.12 (dt,
MHz, CDCl ): δ (ppm) 8.38 (s, 1H), 8.25 (s, 1H), 5.77 – 5.89 (m,
3
J = 5.4, 11.0 Hz, 1H), 2.57 – 2.65 (m, 4H), 2.26 – 2.53 (m, 5H),
1H), 4.74 (s, 1H), 4.60 (s, 1H), 3.93 – 4.10 (m, 2H), 3.11 – 3.16
(m, 1H), 3.01 (d, J = 16.6 Hz, 1H), 2.36 – 2.56 (m, 2H), 2.16 –
2.20 (m, 1H), 0.73 – 1.96 (m, 19H), 1.68 (s, 3H), 1.27 (s, 3H),
2
0
.36 (s, 3H), 0.72 – 1.96 (m, 23H), 1.67 (s, 3H), 0.93 (s, 3H),
.82 (s, 3H), 0.81 (s, 3H), 0.77 (s, 3H), 0.74 (s, 3H); C NMR
13
13
(
101 MHz, CDCl ): δ (ppm) 176.6, 175.8, 172.3, 168.9, 150.8,
1.25 (s, 3H), 1.00 (s, 6H), 0.78 (s, 3H); C NMR (101 MHz,
3
1
8
3
2
45.4, 135.1, 133.7, 129.1, 128.9, 128.9, 128.7, 123.5, 109.4,
1.1, 55.6, 55.4, 53.8, 50.4, 50.1, 48.6, 46.8, 44.7, 42.4, 40.7,
8.4, 38.1, 37.8, 37.7, 37.0, 34.5, 34.2, 33.4, 30.8, 29.8, 29.6,
9.6, 29.4, 27.9, 25.5, 23.6, 20.9, 19.4, 18.1, 16.5, 16.2, 15.8,
CDCl ): δ (ppm) 176.2, 159.8, 151.0, 150.8, 142.4, 141.6, 109.7,
3
80.5, 71.2, 55.8, 53.2, 50.3, 49.0, 48.8, 46.8, 42.7, 40.8, 39.7,
38.3, 37.9, 36.9, 33.7, 33.6, 31.7, 31.0, 29.6, 29.2, 25.8, 24.2,
21.7, 20.3, 19.8, 16.3, 15.9, 14.8; ESIMS: m/z calculated for
+
+
1
4.6; ESIMS: m/z calculated for C H N O (M+H) 879.57,
C H N O (M+H) 528.81, found 528.60.
52
74
6
6
35 49
3
found 879.65.
Preparation of triazole 24a: Procedure similar to that of 19a.
This compound was prepared by the reaction of alkyne 23 with
azide 9a. Yield: 82%; white solid; mp 127 – 129 °C; H NMR
Preparation of succinic acid hemiester 21d: Procedure similar
to that of 21a. Yield: 82%; white solid; mp 114 – 116 °C; H
1
1
NMR (400 MHz, CDCl ): δ (ppm) 9.68 (s, 1H), 7.91 (s, 1H),
(400 MHz, CDCl ): δ 8.32 (s, 1H), 8.20 (s, 1H), 7.98 (s, 1H),
3
3
7
=
.60 (s, 1H), 7.27 – 7.39 (m, 3H), 7.20 – 7.25 (m, 2H), 6.66 (t, J
5.5 Hz, 1H), 4.72 (s, 1H), 4.58 (s, 1H), 4.40 – 4.57 (m, 5H),
7.68 (s, 1H), 7.49 – 7.60 (m, 2H), 7.45 – 7.29 (m, 3H), 6.30 (brs,
1H), 5.29 (s, 2H), 4.68 (s, 1H), 4.55 (s, 1H), 4.37 – 4.49 (m, 2H),
3.78 (s, 3H), 3.07 (dt, J = 4.3, 11.2 Hz, 1H), 2.93 (d, J = 16.4 Hz,
1H), 2.30 – 2.43 (m, 2H), 0.61 – 1.93 (m, 19H), 1.62 (s, 3H),
3
2
0
0
1
1
5
3
2
.73 – 3.85 (m, 2H), 3.34 (s, 2H), 3.12 (dt, J = 4.2, 10.8 Hz, 1H),
.40 – 2.68 (m, 8H), 2.34 (m, 1H), 2.28 (s, 6H), 2.05 (s, 3H),
.72 – 1.98 (m, 23H), 1.66 (s, 3H), 0.92 (s, 3H), 0.81 (s, 9H),
1.20 (s, 3H), 1.15 (s, 3H), 0.91 (s, 3H), 0.73 (s, 3H), 0.66 (s, 3H);
13
13
.77 (s, 3H); C NMR (101 MHz, CDCl ): δ (ppm) 176.5 (2C),
C NMR (101 MHz, CDCl ): δ 176.5, 167.2, 159.8, 151.1,
3
3
72.7, 168.5, 150.8, 145.3, 140.3, 135.5, 130.3, 129.0, 128.3,
27.9, 123.0, 109.4, 80.9, 55.6, 55.4, 55.2, 53.9, 53.5, 53.1, 50.6,
0.5, 50.1, 49.4, 46.7, 44.1, 42.4, 41.4, 40.7, 39.6, 38.4, 38.2,
7.8, 37.7, 37.1, 34.6, 34.2, 33.4, 30.9, 29.4, 27.9, 25.5, 23.7,
150.9, 146.2, 142.5, 141.7 (2C), 133.7 (2C), 130.2, 129.9, 129.2,
125.0, 109.7, 55.9, 53.2, 52.8, 50.3, 49.0, 48.9, 47.1, 46.9, 42.7,
40.8, 39.6, 38.4, 38.0, 36.9, 34.9, 33.7, 33.5, 31.7, 31.1, 29.6,
25.8, 24.2, 21.6, 20.3, 19.8, 16.3, 15.6, 14.8; ESIMS: m/z
+
0.9, 19.4, 18.1, 16.5, 16.2, 15.8, 14.6; ESIMS: m/z calculated
calculated for C H N O (M+H) 745.48, found 745.45.
46
60
6
3
+
for C H N O (M+H) 924.63, found 924.70.
54
81
7
6
Preparation of triazole 24b: Procedure similar to that of 19a.
This compound was prepared by the reaction of alkyne 23 with
azide 9b. Yield: 84%; white solid; mp 131 – 133 °C; H NMR
Preparation of succinic acid hemiester 21e: Procedure similar
1
to that of 21a. Yield: 84%; cream color solid; mp 132 – 134 °C;
1
H NMR (400 MHz, CDCl ): δ 9.64 (m, 1H), 7.94 (s, 1H), 7.64
(400 MHz, CDCl ): δ 8.39 (d, J = 2.4 Hz, 1H), 8.26 (d, J = 2.4
3
3
(
s, 1H), 7.28 – 7.40 (m, 3H), 7.19 – 7.23 (m, 2H), 6.52 (t, J = 5.0
Hz, 1H), 7.63 (s, 1H), 7.29 – 7.48 (m, 5H), 6.95 (brs, 1H), 6.23 –
6.30 (m, 1H), 5.31 – 5.39 (m, 2H), 4.76 (s, 1H), 4.61 (s, 1H),
4.51 (dd, J = 5.4, 15.1 Hz, 1H), 4.44 (dd, J = 5.6, 15.2 Hz, 1H),
3.39 – 3.54 (m, 2H), 3.13 (dt, J = 4.2, 10.9 Hz, 1H), 2.92 – 3.05
(m, 4H), 2.33 – 2.51 (m, 4H), 2.12 – 2.31 (brs, 6H), 0.73 – 1.97
(m, 19H), 1.69 (s, 3H), 1.28 (s, 3H), 1.25 (s, 3H), 0.99 (s, 3H),
Hz, 1H), 4.72 (s, 1H), 4.59 (s, 1H), 4.38 – 4.51 (m, 5H), 3.88 –
3
2
1
.92 (m, 2H), 3.38 (s, 2H), 3.11 (dt, J = 4.4, 11.0 Hz, 1H), 2.40 –
.76 (m, 10H), 2.44 (s, 3H), 2.33 (m, 3H), 0.71 – 1.95 (m, 23H),
.67 (s, 3H), 0.93 (s, 3H), 0.81 (s, 6H), 0.79 (s, 3H), 0.75 (s, 3H);
13
C NMR (101 MHz, CDCl ): δ 176.7 (2C), 172.6, 168.5, 150.7,
3
13
1
8
4
3
1
9
45.7, 141.5, 134.9, 128.9, 128.7, 128.5, 128.3, 123.5, 109.5,
0.9, 55.6, 55.4, 54.2, 53.3, 50.6, 50.4, 50.1, 50.0, 46.8, 44.0,
2.4, 40.7, 39.0, 38.3, 38.2, 37.8, 37.7, 37.1, 34.6, 34.3, 33.4,
0.8, 29.7, 29.4, 27.9, 25.5, 23.6, 20.9, 19.4, 18.1, 16.5, 16.2,
0.86 (s, 3H), 0.75 (s, 3H); C NMR (101 MHz, CDCl ): δ 176.2,
3
159.6, 150.8, 150.7, 145.0, 142.2, 141.4 (2C), 134.8, 134.0,
130.2, 128.8, 128.7, 123.2, 109.4, 55.6, 53.0, 50.0, 48.8, 48.6,
48.6, 46.6, 45.6, 42.4, 40.6, 39.4, 38.2, 37.7, 36.7, 34.7, 33.4,
33.3, 31.4, 30.9, 29.4, 25.6, 24.0, 21.4, 20.0, 19.5, 16.0, 15.4,
+
5.8, 14.6; ESIMS: m/z calculated for C H N O (M+H)
54
79
7
6
+
22.62, found 922.75.
14.6; ESIMS: m/z calculated for C H N O (M+H) 815.57,
50
70
8
2
found 815.30.
Preparation of succinic acid hemiester 21f: Procedure similar
to that of 21a. Yield: 81%; yellow solid; mp 141 – 144 °C; H
1
Preparation of triazole 24c: Procedure similar to that of 19a.
This compound was prepared by the reaction of alkyne 23 with
azide 9c. Yield: 84%; white solid; mp 137 – 140 °C; H NMR
NMR (400 MHz, CDCl ): δ (ppm) 7.64 (d, J = 15.6 Hz, 1H),
3
1
7
6
4
2
2
0
.63 (s, 1H), 7.46 – 7.52 (m, 2H), 7.34 – 7.38 (m, 3H), 6.60 –
.69 (m, 1H), 6.40 (d, J = 15.5 Hz, 1H), 6.26 – 6.34 (m, 1H),
.70 (s, 1H), 4.57 (s, 1H), 4.39 – 4.54 (m, 5H), 3.80 – 3.97 (m,
H), 3.09 (dt, J = 4.1, 11.0 Hz, 1H), 2.59 – 2.70 (m, 4H), 2.22 –
.33 (m, 1H), 0.66 – 1.91 (m, 23H), 1.65 (s, 3H), 0.91 (s, 3H),
(400 MHz, CDCl ): δ (ppm) 8.33 (d, J = 2.4 Hz, 1H), 8.20 (d, J =
3
2.4 Hz, 1H), 7.55 (s, 1H), 7.29 – 7.41 (m, 5H), 6.80 (s, 1H), 6.20
- 6.30 (m, 1H), 5.35 (s, 2H), 4.70 (s, 1H), 4.56 (s, 1H), 4.46 (dd,
J = 5.5, 15.0 Hz, 1H), 4.36 (dd, J = 5.5, 15.0 Hz, 1H), 3.60 (brs,
4H), 3.12 (dt, J = 4.3, 11.2 Hz, 1H), 3.01 (d, J = 16.6 Hz, 1H),
2.05 – 2.39 (m, 9H), 0.64 – 1.89 (m, 19H), 1.63 (s, 3H), 1.22 (s,
13
.80 (s, 3H), 0.79 (s, 6H), 0.71 (s, 3H); C NMR (101 MHz,
CDCl ): δ (ppm) 176.9 (2C), 172.2, 166.6, 150.7, 145.3, 141.8,
3