Organic & Biomolecular Chemistry
Paper
J = 7.2 Hz, 1H); 3.90–3.98 (m, 2H); 4.13–4.18 (m, 1H); 4.30–4.37 127.4, 128.3, 128.8, 135.8, 137.5, 140.9, 143.5, 176.9,
(m, 1H); 4.50–4.58 (m, 1H); 4.62 (d, J = 4.0 Hz, 1H); 4.64 (d, J = 198.0 ppm. HRMS (EI) exact mass calc. for C32H32ClN5O6SNa:
12.0 Hz, 1H); 4.73 (d, J = 13.6 Hz, 1H); 4.92 (dd, J = 1.6, 14.0 672.1660 (M+) found 672.1661. [α]2D5.8 −5.04 (c 0.2, CHCl3).
Hz, 1H); 5.86 (d, J = 4.0 Hz, 1H); 6.88 (d, J = 8.0 Hz, 1H); 7.05
Macrocycle 10e. Yield: 74% (0.23 g). White crystalline solid.
(t, J = 7.6 Hz, 1H); 7.29 (d, J = 7.6 Hz, 1H); 7.35–7.39 (m, 1H); mp 144–146 °C. IR (KBr): 1044, 1380, 1622, 1731, 2632 cm−1
.
7.60 (s, 1H); 13C NMR (75 MHz, CDCl3): 13.8, 24.9, 26.2, 26.6, 1H NMR (400 MHz, CDCl3): δ 0.93 (t, J = 7.2 Hz, 3H); 1.32 (s,
28.5, 39.5, 46.7, 47.4, 48.6, 55.8, 60.7, 61.2, 71.2, 72.3, 76.6, 3H); 1.49 (s, 3H); 2.08 (s, 3H); 3.21–3.25 (m, 1H); 3.27 (t, J = 7.2
79.2, 80.1, 82.0, 103.8, 107.4, 111.6, 122.7, 126.0, 126.1, 126.8, Hz, 1H); 3.57 (t, J = 7.2 Hz, 1H); 3.62–3.70 (m, 3H); 3.87–3.95
129.7, 141.7, 173.3, 178.2 ppm. HRMS (EI) exact mass calc. for (m, 1H); 3.97 (d, J = 3.2 Hz, 1H); 4.15 (t, J = 3.2 Hz, 1H);
C29H35N5O7H: 566.2615 (M + H) found 566.2611. [α]2D6.6 −9.43 4.34–4.41 (m, 1H); 4.54–4.61 (m, 1H); 4.64–4.65 (m, 1H); 4.66
(c 0.2, CHCl3).
Macrocycle 10b. Yield: 72% (0.23 g). White crystalline solid. 14.0 Hz, 1H); 5.87 (d, J = 4.0 Hz, 1H); 6.86, (d, J = 8.0 Hz, 1H);
mp 183–186 °C. IR (KBr): 1055, 1378, 1622, 1718, 2634 cm−1
7.05–7.09 (m, 1H); 7.14–7.16 (m, 1H); 7.32–7.36 (m, 1H); 7.70
(d, J = 13.2 Hz, 1H); 4.75 (d, J = 13.2 Hz, 1H); 4.92 (dd, J = 1.2,
.
1H NMR (500 MHz, CDCl3): δ 1.26 (s, 3H); 1.44 (s, 3H); (s, 1H). 13C NMR (75 MHz, CDCl3): 12.8, 25.1, 25.6, 34.3, 38.1,
1.71–1.80 (m, 2H); 1.84–1.90 (m, 1H); 1.99–2.02 (m, 1H); 38.3, 46.4, 53.6, 59.5, 59.7, 60.2, 72.1, 78.3, 80.5, 81.2, 102.9,
2.10–2.13 (m, 1H); 2.68 (t, J = 7.5 Hz, 1H); 3.26–3.30 (m, 2H); 106.1, 110.5, 122.1, 124.4, 125.2, 125.6, 128.5, 140.4, 141.9,
4.04 (t, J = 2.5 Hz, 1H); 4.30 (d, J = 2.0 Hz, 1H); 4.33–4.37 (m, 170.9, 177.8 ppm. HRMS (EI) exact mass calc. for
1H); 4.41–4.44 (m, 2H); 4.51 (d, J = 12.5 Hz, 1H); 4.62 (d, J = C27H33N5O7H: 540.2458 (M + H) found 540.2455. [α]2D6.3 −7.84
4 Hz, 1H); 4.72–4.75 (m, 1H); 4.91 (d, J = 12.5 Hz, 1H); 4.96 (d, (c 0.2, CHCl3).
J = 7.0 Hz, 1H); 5.69 (d, J = 4.0 Hz, 1H); 6.57 (d, J = 8.0 Hz, 1H);
Macrocycle 10f. Yield: 71% (0.22 g). White crystalline solid.
6.74 (t, J = 7.5 Hz, 1H); 7.04 (t, J = 7.5 Hz, 1H); 7.08 (d, J = mp 155–157 °C. IR (KBr): 1048, 1376, 1632, 1731, 2624 cm−1
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7.5 Hz, 1H); 7.16–7.19 (m, 2H); 7.21–7.23 (m, 2H); 7.62 (s, 1H). 1H NMR (500 MHz, CDCl3): δ 1.26 (s, 3H); 1.44 (s, 3H); 2.01 (s,
13C NMR (75 MHz, CDCl3): 13.1, 25.1, 25.5, 28.0, 39.1, 46.8, 3H); 3.37–3.47 (m, 2H); 3.52–3.59 (m, 1H); 3.61–3.63 (m, 1H);
47.1, 49.1, 53.0, 59.4, 61.1, 67.4, 71.2, 76.2, 77.1, 80.3, 81.6, 4.10 (t, J = 2.5 Hz, 1H); 4.16 (d, J = 3.0 Hz, 1H); 4.46–4.48 (m,
102.3, 106.2, 110.5, 121.6, 123.6, 124.1, 127.4, 127.6, 128.4, 2H); 4.53–4.54 (m, 1H); 4.58 (d, J = 13.0 Hz, 1H); 4.60 (d, J = 4.0
136.2, 137.6, 141.3, 143.8, 177.0, 200.9 ppm. HRMS (EI) exact H, 1H); 4.79–4.81 (m, 1H); 4.84 (d, J = 13.0 Hz, 1H); 5.71 (d, J =
mass calc. for C33H34ClN5O6H: 632.2275 (M + H) found 4.0 Hz, 1H); 6.66 (d, J = 7.5 Hz, 1H); 6.78 (t, J = 7.5 Hz, 1H);
632.2274. [α]2D8.4 −4.2 (c 0.2, CHCl3).
Macrocycle 10c. Yield: 70% (0.24 g). White crystalline solid. (d, J = 8.5 Hz, 2H); 7.63 (s, 1H). 13C NMR (75 MHz, CDCl3):
mp 196–198 °C. IR (KBr): 1050, 1388, 1632, 1724, 2638 cm−1
24.3, 24.8, 33.1, 37.5, 38.4, 45.8, 52.0, 57.8, 59.5, 71.9, 79.1,
6.92–6.93 (m, 1H); 7.09–7.12 (m, 1H); 7.19–7.24 (m, 2H); 7.48
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1H NMR (300 MHz, CDCl3): δ 0.84 (t, J = 7.2 Hz, 3H); 1.27 (s, 79.6, 80.2, 101.5, 105.5, 109.7, 121.5, 123.0, 123.4, 125.2, 126.7,
3H); 1.45 (s, 3H); 2.81 (d, J = 6.6 Hz, 1H); 3.03–3.08 (m, 1H); 127.8, 128.2, 134.9, 136.9, 140.0, 142.3, 176.4, 198.7 ppm.
3.19 (t, J = 9.9 Hz, 1H); 3.32–3.42 (m, 2H); 3.54 (d, J = 9.3 Hz, HRMS (EI) exact mass calc. for C31H32ClN5O6H: 606.2119 (M +
1H); 3.68 (d, J = 14.4 Hz, 1H); 3.73–3.79 (m, 1H); 3.82–3.88 (m, H) found 606.2112. [α]2D5.4 −6.59 (c 0.2, CHCl3).
2H); 3.98 (d, J = 9.3 Hz, 1H); 4.32–4.36 (m, 1H); 4.41–4.45 (m,
Macrocycle 11a. Yield: 72% (0.23 g). White crystalline solid.
1H); 4.51–4.61 (m, 1H); 4.61–4.73 (m, 3H); 4.89 (d, J = 13.8 Hz, mp 166–168 °C. IR (KBr): 1038, 1389, 1632, 1718, 2639 cm−1
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1H); 5.87 (d, J = 3.9 Hz, 1H); 6.80 (d, J = 7.8 Hz, 1H); 7.02 (t, J = 1H NMR (500 MHz, CDCl3): δ 0.73 (t, J = 7.5 Hz, 3H); 1.24 (s,
7.5 Hz, 1H); 7.31 (d, J = 7.8 Hz, 1H); 7.36 (d, J = 7.2 Hz, 1H); 3H); 1.47 (s, 3H); 1.63 (d, J = 6.5 Hz, 1H); 1.69–1.77 (m, 1H);
7.89 (s, 1H). 13C NMR (75 MHz, CDCl3): 12.7, 25.2, 26.0, 34.0, 1.79–1.87 (m, 2H); 2.16–2.21(m, 1H); 2.58–2.63 (m, 1H);
42.5, 46.7, 51.6, 55.3, 60.2, 60.3, 72.4, 77.4, 78.0, 81.8, 82.9, 2.68–2.71 (m, 1H); 3.12–3.16 (m, 2H); 3.54–3.62 (m, 2H);
103.6, 106.3, 110.6, 122.1, 123.9, 125.0, 129.1, 140.6, 141.5, 4.16–4.17 (m, 1H); 4.24–4.27 (m, 1H); 4.44 (d, J = 14.0 Hz, 1H);
170.1, 178.4 ppm. HRMS (EI) exact mass calc. for 4.56 (d, J = 14.0 Hz, 1H); 4.62–4.66 (m, 2H); 4.84 (d, J = 14.0
C28H33N5O7SH: 584.2179 (M + H) found 584.2171. [α]2D5.5 −6.18 Hz, 1H); 5.07 (d, J = 14.0 Hz, 1H); 5.71 (d, J = 14.0 Hz, 1H); 5.78
(c 0.2, CHCl3).
Macrocycle 10d. Yield: 76% (0.25 g). White crystalline solid. J = 8.0 Hz, 1H); 7.11 (d, J = 7.5 Hz, 1H); 7.15 (d, J = 7.5 Hz, 1H);
mp 148–151 °C. IR (KBr): 1055, 1373, 1628, 1730, 2632 cm−1
7.20–7.26 (m, 2H); 7.33 (t, J = 8.0 Hz, 1H); 7.56 (d, J = 8.0 Hz,
(d, J = 4.0 Hz, 1H); 6.89 (s, 1H); 6.92 (t, J = 7.5 Hz, 1H); 7.07 (d,
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1H NMR (500 MHz, CDCl3): δ 1.26 (s, 3H); 1.44 (s, 3H); 1H). 13C NMR (75 MHz, CDCl3): 12.8, 25.0, 25.5, 26.1, 29.4,
2.93–2.96 (m, 2H); 3.03–3.33 (m, 1H); 3.39–3.40 (m, 1H); 42.8, 47.3, 47.8, 53.4, 57.9, 59.4, 59.9, 71.1, 71.5, 78.2, 79.5,
3.54–3.58 (m, 2H); 4.13 (t, J = 2.5 Hz, 1H); 4.25 (d, J = 2.5 Hz, 83.4, 103.5, 107.9, 110.7, 121.0, 122.4, 125.3, 125.8, 126.6,
1H); 4.43–4.47 (m, 2H); 4.54 (d, J = 12.5 Hz, 1H); 4.63–4.64 (m, 127.7, 128.4, 128.6, 131.0, 134.0, 135.9, 141.7, 142.0, 171.5,
2H); 4.76–4.78 (m, 1H); 4.89 (d, J = 12.5 Hz, 1H); 4.98 (d, J = 5.0 177.1 ppm. HRMS (EI) exact mass calc. for C35H39N5O7H:
Hz, 1H); 5.71 (d, J = 4.0 Hz, 1H); 6.60 (d, J = 7.5 Hz, 1H); 6.77 642.2928 (M + H) found 642.2926. [α]2D8.8 −8.74 (c 0.2, CHCl3).
(t, J = 7.5 Hz, 1H); 6.98 (d, J = 7.0 Hz, 1H); 7.05–7.08 (m, 1H);
Macrocycle 11b. Yield: 69% (0.22 g). White crystalline solid.
7.17–7.21 (m, 4H); 7.66 (s, 1H). 13C NMR (75 MHz, CDCl3): mp 170–172 °C. IR (KBr): 1050, 1398, 1623, 1716, 2663 cm−1
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25.1, 25.6, 31.4, 38.7, 42.3, 44.4, 47.1, 56.3, 61.0, 67.4, 70.7, 1H NMR (300 MHz, CDCl3): δ 1.27 (s, 3H); 1.47 (s, 3H);
78.3, 80.6, 81.3, 102.4, 106.3, 110.6, 122.1, 122.9, 124.0, 126.3, 2.20–2.34 (m, 2H); 2.59–2.64 (m, 1H); 2.75–2.76 (m, 1H);
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