I
D.-M. Huang et al.
Paper
Synthesis
13C NMR (100 MHz, CDCl3): = 170.2, 156.8, 156.5, 152.7, 148.8 (2C),
137.2, 137.1, 136.8, 136.7, 131.0, 128.69 (2C), 128.62 (2C), 128.51
(2C), 128.46 (2C), 128.1, 128.0, 127.82, 127.78, 127.39 (2C), 127.32
(2C), 127.29 (2C), 127.22 (2C), 119.3, 114.8, 113.1, 109.9, 101.7, 91.2,
77.9, 71.3 (2C), 70.8, 70.1, 68.7, 54.6, 23.4, 21.1.
127.78, 127.4 (2C), 127.34 (2C), 127.28 (2C), 127.2 (2C), 119.5, 115.0,
113.2, 110.0, 101.8, 91.3, 78.2, 71.32, 71.30, 70.8, 70.1, 69.5, 54.7,
23.8.
IR (film): 3262, 2934, 1743, 1622, 1521, 1499, 1269, 1119, 1020, 745,
694 cm–1
.
IR (film): 3259, 2968, 2849, 1742, 1603, 1501, 1297, 1231, 1143,
HRMS (ESI): m/z [M + H]+ calcd for C51H45O8: 785.3109; found:
785.3113.
1019, 733, 679 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C46H43O8: 723.2952; found:
723.2950.
5,7,3′,4′-Tetra-O-benzyl-8-methylol-epicatechin (11g)
Yield: 64.7 mg (95%); colorless oil; []D25 –35.0 (c = 1.00, CHCl3).
3-Methoxymethoxy-5,7,3′,4′-tetra-O-benzyl-8-methylol-catechin
(11d)
Yield: 68.1 mg (94%); colorless oil; []D25 –16.7 (c = 1.00, CHCl3).
1H NMR (400 MHz, CDCl3): = 7.48–7.32 (m, 20 H), 7.14 (s, 1 H), 7.01
(s, 2 H), 6.27 (s, 1 H), 5.22–5.21 (m, 4 H), 5.09 (s, 2 H), 5.05 (s, 2 H),
4.98 (s, 1 H), 4.82 (d, J = 5.0 Hz, 2 H), 4.25 (s, 1 H), 3.04 (d, J = 17.1 Hz,
1 H), 2.95 (dd, J = 17.2, 4.3 Hz, 1 H).
13C NMR (100 MHz, CDCl3): = 157.5, 156.5, 153.2, 149.1, 149.0,
137.3, 137.2, 136.93, 136.90, 131.3, 128.7 (2C), 128.6 (2C), 128.5 (4C),
128.2, 128.03, 127.95, 127.8, 127.4 (2C), 127.3 (4C), 127.1 (2C), 119.2,
115.2, 113.4, 110.2, 101.5, 91.6, 78.4, 71.4 (2C), 70.9, 70.1, 66.0, 54.6,
28.1.
1H NMR (400 MHz, CDCl3): = 7.47–7.30 (m, 20 H), 7.02 (s, 1 H), 6.93
(s, 2 H), 6.25 (s, 1 H), 5.18–5.17 (m, 4 H), 5.07–5.05 (m, 4 H), 4.92 (d,
J = 7.2 Hz, 1 H), 4.77 (s, 2 H), 4.54 (d, J = 6.8 Hz, 1 H), 4.31 (d, J = 6.8 Hz,
1 H), 4.03–3.98 (m, 1 H), 3.11 (s, 3 H), 2.97 (dd, J = 16.6, 5.3 Hz, 1 H),
2.73 (dd, J = 16.5, 7.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): = 156.8, 156.3, 153.2, 148.8 (2C), 137.24,
137.18, 136.97, 136.93, 132.2, 128.67 (2C), 128.61 (2C), 128.49 (2C),
128.47 (2C), 128.03, 127.96, 127.82, 127.80, 127.4 (2C), 127.31 (2C),
127.30 (2C), 127.1 (2C), 119.9, 114.9, 113.7, 110.0, 102.6, 95.0, 91.4,
79.6, 72.0, 71.34, 71.28, 70.8, 70.1, 55.3, 54.7, 25.3.
IR (film): 3255, 2944, 1618, 1520, 1459, 1251, 1238, 1111, 1024, 738,
703 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C44H41O7: 681.2847; found:
681.2849.
IR (film): 3231, 2931, 1621, 1451, 1261, 1230, 1116, 1028, 742, 702
cm–1
.
3,5,7,3′,4′-Penta-O-benzyl-8-methylol-epicatechin (11h)
Yield: 71.7 mg (93%); colorless oil; []D25 –37.8 (c = 1.00, CHCl3).
1H NMR (400 MHz, CDCl3): = 7.50–7.31 (m, 22 H), 7.20–7.15 (m,
3 H), 7.03–6.94 (m, 4 H), 6.25 (s, 1 H), 5.22 (s, 2 H), 5.10–5.05 (m, 7 H),
4.82 (d, J = 3.0 Hz, 2 H), 4.44 (d, J = 12.5 Hz, 1 H), 4.32 (d, J = 12.4 Hz,
1 H), 3.96 (s, 1 H), 3.00 (d, J = 16.9 Hz, 1 H), 2.82 (dd, J = 16.9, 3.9 Hz,
1 H).
13C NMR (100 MHz, CDCl3): = 157.1, 156.3, 153.6, 148.7, 148.3,
138.0, 137.4, 137.3, 137.04, 136.99, 132.0, 128.66 (2C), 128.62 (2C),
128.52 (2C), 128.45 (2C), 128.2 (2C), 128.01, 127.98, 127.8, 127.72,
127.67 (2C), 127.5, 127.33 (4C), 127.30 (2C), 127.2 (2C), 119.5, 114.7,
113.6, 110.1, 102.0, 91.3, 78.0, 72.3, 71.4, 71.3, 71.0, 70.8, 70.1, 54.8,
24.5.
HRMS (ESI): m/z [M + H]+ calcd for C46H45O8: 725.3109; found:
725.3108.
3-Propoxy-5,7,3′,4′-tetra-O-benzyl-8-methylol-catechin (11e)
Yield: 68.7 mg (95%); colorless oil; []D25 –16.0 (c = 1.00, CHCl3).
1H NMR (400 MHz, CDCl3): = 7.48–7.30 (m, 20 H), 7.04 (s, 1 H), 6.95
(s, 2 H), 6.25 (s, 1 H), 5.20–5.18 (m, 4 H), 5.07–5.06 (m, 4 H), 4.81 (d,
J = 7.7 Hz, 1 H), 4.76 (s, 2 H), 3.63–3.58 (m, 1 H), 3.33–3.27 (m, 1 H),
3.05–2.96 (m, 2 H), 2.67 (dd, J = 16.5, 8.4 Hz, 1 H), 1.38 (q, J = 6.9 Hz,
2 H), 0.73 (t, J = 7.4 Hz, 3 H).
13C NMR (100 MHz, CDCl3): = 156.8, 156.2, 153.5, 148.83, 148.75,
137.32, 137.28, 137.02, 136.98, 132.6, 128.68 (2C), 128.63 (2C),
128.51 (2C), 128.48 (2C), 128.04, 127.98, 127.82, 127.79, 127.42 (2C),
127.35 (2C), 127.32 (2C), 127.2 (2C), 120.2, 114.9, 113.9, 110.0, 103.0,
91.3, 80.0, 75.3, 71.7, 71.39, 71.30, 70.9, 70.1, 54.8, 25.8, 23.0, 10.4.
IR (film): 3247, 2931, 2870, 1635, 1589, 1281, 1230, 1143, 1021, 720,
674 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C51H47O7: 771.3316; found:
771.3318.
IR (film): 3265, 2955, 2881, 1625, 1481, 1282, 1232, 1149, 1047, 910,
765, 691 cm–1
.
HRMS (ESI): m/z [M + H]+ calcd for C47H47O7: 723.3316; found:
723.3321.
5,7,3′,4′-Tetra-O-benzyl-3-O-(3,4,5-tri-O-benzylgalloyl)-8-methyl-
ol-epicatechin (11i)
Yield: 105.9 mg (96%); colorless oil; []D25 –48.7 (c = 1.00, CHCl3).
3-Benzoyloxy-5,7,3′,4′-tetra-O-benzyl-8-methylol-catechin (11f)
1H NMR (400 MHz, CDCl3): = 7.41–7.25 (m, 37 H), 7.08 (s, 1 H), 6.96
(d, J = 8.1 Hz, 1 H), 6.87 (d, J = 8.2 Hz, 1 H), 6.31 (s, 1 H), 5.64 (s, 1 H),
5.16–5.05 (m, 13 H), 4.91–4.87 (m, 4 H), 3.12–3.11 (m, 2 H).
25
Yield: 73.0 mg (93%); yellow solid; mp 99–100 °C; []D –20.5 (c =
1.00, CHCl3).
1H NMR (400 MHz, CDCl3): = 7.95 (d, J = 7.6 Hz, 2 H), 7.55 (t, J =
7.4 Hz, 1 H), 7.46–7.31 (m, 22 H), 7.03 (d, J = 1.2 Hz, 1 H), 6.95 (dd, J =
8.3, 1.5 Hz, 1 H), 6.90 (d, J = 8.3 Hz, 1 H), 6.29 (s, 1 H), 5.58–5.54 (m,
1 H), 5.26 (d, J = 6.1 Hz, 1 H), 5.14–5.05 (m, 8 H), 4.82 (s, 2 H), 3.02
(dd, J = 17.0, 5.3 Hz, 1 H), 2.91 (dd, J = 17.0, 6.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): = 165.6, 156.8, 156.5, 152.9, 148.9 (2C),
137.2, 137.1, 136.9, 136.8, 133.1, 131.1, 129.9, 129.7 (2C), 128.7 (2C),
128.6 (2C), 128.48 (2C), 128.45 (2C), 128.37 (2C), 128.1, 128.0, 127.80,
13C NMR (100 MHz, CDCl3): = 165.0, 157.1, 156.4, 153.6, 152.4 (2C),
148.9 (2C), 142.5, 137.4, 137.1, 136.9, 136.8, 136.7, 136.6 (2C), 130.9,
128.7 (2C), 128.6 (2C), 128.53 (6C), 128.49 (2C), 128.42 (2C), 128.2
(2C), 128.1, 128.03, 127.98 (2C), 127.94, 127.80, 127.76, 127.6 (4C),
127.3 (2C), 127.24 (4C), 127.19 (2C), 124.9, 119.7, 114.7, 113.4, 110.1,
109.0 (2C), 101.3, 91.2, 77.6, 75.1, 71.26, 71.22, 71.0 (2C), 70.8, 70.1,
68.3, 54.7, 29.7.
IR (film): 3261, 2955, 1740, 1628, 1470, 1275, 1230, 1141, 1012, 760,
685 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–O