Organic & Biomolecular Chemistry
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OH), 2.84–2.97 (m, 2H; HB-1′, HB-5′), 3.04–3.13 (m, 2H; HB-1, MeOH 98 : 2). [α]2D0 = +3 (c 1.0, CHCl3). 1H-NMR (CDCl3,
HB-5), 3.36 (t, J = 6.9 Hz, 1H; H-3′), 3.39 (t, J = 8.9 Hz, 1H; H-3), 300 MHz) δ 1.22–1.42 (m, 4H; CH2-11, CH2-12), 1.50–1.62 (m,
3.52–3.75 (m, 8H; H-2, H-2′, H-4, H-4′, 2 × NCH2Ph), 4.14–4.19 2H; CH2-13), 1.71–1.84 (m, 2H; CH2-10), 1.93–2.04 (m, 2H;
(m, 2H; CH2-9 or CH2-18), 4.25 (t, J = 7.2 Hz, 2H; CH2-9 or HA-1, HA-5), 2.19–2.36 (m, 2H; HA-1′, HA-5′), 2.83–2.99 (m, 2H;
CH2-18), 4.60 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.66 (d, J = HB-1′, HB-5′), 3.04–3.15 (m, 2H; HB-1, HB-5), 3.36 (t, J = 7.0 Hz,
12.3 Hz, 1H; HA-6′), 4.67 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.68 (d, 1H; H-3′), 3.40 (t, J = 8.9 Hz, 1H; H-3), 3.43 (t, J = 6.4 Hz, 2H;
J = 11.7 Hz, 1H; OCH2Ph), 4.746 (d, J = 12.3 Hz, 1H; HB-6′), CH2-14), 3.50–3.76 (m, 16H; H-2, H-2′, H-4, H-4′, CH2-15, CH2-
4.749 (d, J = 12.6 Hz, 1H; HA-6), 4.79 (d, J = 12.6 Hz, 1H; HB-6), 16, CH2-17, CH2-18, 2 × NCH2Ph), 3.83 (t, J = 5.1 Hz, 2H; CH2-
4.837 (d, J = 11.2 Hz, 1H; OCH2Ph), 4.842 (d, J = 11.7 Hz, 1H; 19), 4.11–4.23 (m, 2H; CH2-9), 4.48 (t, J = 5.1 Hz, 2H; CH2-20),
OCH2Ph), 4.92 (d, J = 11.2 Hz, 1H; OCH2Ph), 7.22–7.40 (m, 4.62 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.67 (d, J = 12.3 Hz, 1H; HA-
27H; H-8, H-8′, HAr). 13C-NMR (CDCl3, 100 MHz) δ 26.5, 26.6, 6′), 4.68 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.69 (d, J = 11.7 Hz, 1H;
29.0, 29.4, 30.3, 30.4 (C-10, C-11, C-12, C-13, C-14, C-15, C-16, OCH2Ph), 4.75 (d, J = 12.3 Hz, 1H; HB-6′), 4.73–4.82 (m, 2H;
C-17), 50.3, 50.4 (C-9, C-18), 54.5 (C-5′), 55.9, 56.0 (C-1, C-5), CH2-6), 4.85 (d, J = 11.2 Hz, 1H; OCH2Ph), 4.86 (d, J = 11.7 Hz,
56.6 (C-1′), 62.1, 62.2 (2 × NCH2Ph), 63.7 (C-6′), 64.6 (C-6), 69.5 1H; OCH2Ph), 4.94 (d, J = 11.2 Hz, 1H; OCH2Ph), 7.22–7.41 (m,
(C-4′), 73.0, 74.0, 75.3 (3 × OCH2Ph), 77.8 (C-2′), 78.7, 78.9 (C-2, 26H; H-8, HAr), 7.63 (s, 1H; H-8′). 13C-NMR (CDCl3, 75.5 MHz)
C-4), 83.0 (C-3′), 86.3 (C-3), 122.2 (C-8, C-8′), 127.4, 127.5, δ 25.6, 26.4 (C-11, C-12), 29.5, 30.2 (C-10, C-13), 50.1, 50.3 (C-9,
127.7, 127.77, 127.82, 127.9, 128.4, 128.45, 128.47, 128.6, C-20), 54.6 (C-5′), 55.9, 56.0 (C-1, C-5), 56.6 (C-1′), 62.1, 62.2
129.0, 129.1 (25 × CHAr), 137.8, 138.6, 138.8, 139.4 (5 × CAr), (2 × NCH2Ph), 63.5 (C-6′), 64.5 (C-6), 69.47 (C-4′), 69.51 (C-19),
145.3 (C-7′), 145.7 (C-7). IR (neat) 3400 cm−1 (O–H). HRMS 70.2, 70.5, 70.6, 70.7 (C-15, C-16, C-17, C-18), 71.2 (C-14), 72.9,
(ESI) m/z calculated for C61H77N8O6: 1017.596 [M + H]+; found 74.0, 75.3 (3 × OCH2Ph), 77.8 (C-2′), 78.7, 78.9 (C-2, C-4), 82.9
1017.587.
(C-3′), 86.3 (C-3), 122.2 (C-8), 123.6 (C-8′), 127.28, 127.30,
127.5, 127.7, 127.76, 127.78, 127.81, 128.36, 128.37, 128.41,
128.6, 128.9, 129.0 (25 × CHAr), 137.8, 137.9, 138.6, 138.8,
Compound 37c
Compound 37c (69 mg, 61%) was prepared by general pro- 139.3 (5 × CAr), 145.1 (C-7′), 145.6 (C-7). IR (neat) 3416 cm−1
cedure A, starting from 36c (66 mg, 0.11 mmol) and 23 (1.1 (O–H). HRMS (ESI) m/z calculated for C63H81N8O9: 1093.612
eq., 52 mg, 0.12 mmol). Pale yellow oil. Rf 0.24 (CH2Cl2/MeOH [M + H]+; found 1093.609.
96 : 4). [α]2D0 = +1 (c 1.0, CHCl3). 1H-NMR (CDCl3, 400 MHz)
Compound 37e
δ
1.24–1.44 (m, 8H; CH2-11, CH2-12, CH2-17, CH2-18),
1.51–1.61 (m, 4H; CH2-13, CH2-16), 1.74–1.89 (m, 4H; CH2-10, Compound 37e (115 mg, 83%) was prepared by general pro-
CH2-19), 1.94–2.03 (m, 2H; HA-1, HA-5), 2.19–2.35 (m, 2H; cedure A, starting from 36e (98 mg, 0.12 mmol) and (+)-14 (1.1
HA-1′, HA-5′), 2.85–3.01 (m, 3H; HB-1′, HB-5′, OH), 3.06–3.15 eq., 45 mg, 0.13 mmol). Colorless oil. Rf 0.22 (CH2Cl2/MeOH
1
(m, 2H; HB-1, HB-5), 3.33–3.45 (m, 6H; H-3, H-3′, CH2-14, CH2- 98 : 2). [α]2D0 = +2 (c 1.0, CHCl3). H-NMR (CDCl3, 300 MHz) δ
15), 3.52–3.77 (m, 8H; H-2, H-2′, H-4, H-4′, 2 × NCH2Ph), 1.20–1.39 (m, 12H; CH2-11, CH2-12, CH2-13, CH2-14, CH2-15,
4.16–4.21 (m, 2H; CH2-9 or CH2-20), 4.26 (t, J = 7.2 Hz, 2H; CH2-16), 1.53–1.65 (m, 2H; CH2-17), 1.72–1.84 (m, 2H; CH2-
CH2-9 or CH2-20), 4.63 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.68 (d, 10), 1.94–2.05 (m, 2H; HA-1, HA-5), 2.19–2.35 (m, 2H; HA-1′,
J = 12.3 Hz, 1H; HA-6′), 4.69 (d, J = 11.6 Hz, 1H; OCH2Ph), 4.71 HA-5′), 2.85–3.00 (m, 2H; HB-1′, HB-5′), 3.05–3.16 (m, 2H; HB-1,
(d, J = 11.7 Hz, 1H; OCH2Ph), 4.76 (d, J = 12.3 Hz, 1H; HB-6′), HB-5), 3.37 (t, J = 7.1 Hz, 1H; H-3′), 3.42 (t, J = 8.9 Hz, 1H; H-3),
4.77 (d, J = 12.6 Hz, 1H; HA-6), 4.80 (d, J = 12.6 Hz, 1H; HB-6), 3.46 (t, J = 6.8 Hz, 2H; CH2-18), 3.52–3.77 (m, 20H; H-2, H-2′,
4.86 (d, J = 11.2 Hz, 1H; OCH2Ph), 4.87 (d, J = 11.7 Hz, 1H; H-4, H-4′, CH2-19, CH2-20, CH2-21, CH2-22, CH2-23, CH2-24,
OCH2Ph), 4.95 (d, J = 11.2 Hz, 1H; OCH2Ph), 7.23–7.42 (m, 2 × NCH2Ph), 3.84 (t, J = 5.1 Hz, 2H; CH2-25), 4.13–4.24 (m,
27H; H-8, H-8′, HAr). 13C-NMR (CDCl3, 75.5 MHz) δ 25.7, 26.4 2H; CH2-9), 4.49 (t, J = 5.1 Hz, 2H; CH2-26), 4.63 (d, J = 11.6 Hz,
(C-11, C-12, C-17, C-18), 29.6, 30.22, 30.24 (C-10, C-13, C-16, 1H; OCH2Ph), 4.69 (d, J = 12.3 Hz, 1H; HA-6′), 4.70 (d, J = 11.6
C-19), 50.15, 50.23 (C-9, C-20), 54.6 (C-5′), 55.9, 56.0 (C-1, C-5), Hz, 1H; OCH2Ph), 4.70 (d, J = 11.7 Hz, 1H; OCH2Ph), 4.76 (d,
56.7 (C-1′), 62.1, 62.2 (2 × NCH2Ph), 63.6 (C-6′), 64.5 (C-6), 69.5 J = 12.3 Hz, 1H; HB-6′), 4.74–4.84 (m, 2H; CH2-6), 4.87 (d, J =
(C-4′), 70.7 (C-14, C-15), 72.9, 74.0, 75.3 (3 × OCH2Ph), 77.8 11.2 Hz, 1H; OCH2Ph), 4.88 (d, J = 11.7 Hz, 1H; OCH2Ph), 4.95
(C-2′), 78.6, 78.9 (C-2, C-4), 83.0 (C-3′), 86.2 (C-3), 122.1 (C-8, (d, J = 11.2 Hz, 1H; OCH2Ph), 7.22–7.42 (m, 26H; H-8, HAr),
C-8′), 127.3, 127.4, 127.6, 127.68, 127.74, 127.8, 128.3, 128.35, 7.65 (s, 1H; H-8′). 13C-NMR (CDCl3, 75.5 MHz) δ 26.1, 26.5,
128.40, 128.5, 128.9, 129.0 (25 × CHAr), 137.7, 137.9, 138.6, 29.0, 29.36, 29.44, 29.5, 29.6, 30.2 (C-10, C-11, C-12, C-13, C-14,
138.8, 139.3 (5 × CAr), 145.3 (C-7′), 145.6 (C-7). IR (neat) C-15, C-16, C-17), 50.2 (C-9, C-26), 54.6 (C-5′), 55.85, 55.92 (C-1,
3400 cm−1 (O–H). HRMS (ESI) m/z calculated for C63H81N8O7: C-5), 56.6 (C-1′), 62.0, 62.1 (2 × NCH2Ph), 63.4 (C-6′), 64.4 (C-6),
1061.622 [M + H]+; found 1061.612.
69.5 (C-4′, C-25), 70.1, 70.5, 70.56, 70.59, 70.63 (C-19, C-20,
C-21, C-22, C-23, C-24), 71.5 (C-18), 72.9, 74.0, 75.2 (3 ×
OCH2Ph), 77.8 (C-2′), 78.6, 78.8 (C-2, C-4), 83.0 (C-3′), 86.2
Compound 37d
Compound 37d (74 mg, 84%) was prepared by general pro- (C-3), 122.1 (C-8), 123.6 (C-8′), 127.2, 127.3, 127.4, 127.6,
cedure A, starting from 36d (60 mg, 0.081 mmol) and (+)-14 127.70, 127.74, 127.8, 128.30, 128.32, 128.4, 128.5, 128.8, 128.9
(1.1 eq., 31 mg, 0.088 mmol). Colorless oil. Rf 0.21 (CH2Cl2/ (25 × CHAr), 137.7, 137.9, 138.5, 138.8, 139.3 (5 × CAr), 145.0
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