M. Ao et al.
Bioorganic Chemistry 113 (2021) 104961
53.1%; Mp: 122–123 ◦C. 1H NMR (600 MHz, CDCl3): δ 12.90 (s, 1H),
7.93 (d, J = 15.3 Hz, 1H), 7.87 (d, J = 1.8 Hz, 1H), 7.49–7.56 (m, 2H),
7.38–7.45 (m, 2H), 7.14 (d, J = 8.3 Hz, 1H), 6.97 (d, J = 8.3 Hz, 1H),
5.30 (s, 2H), 3.55 (s, 3H), 2.09–2.18 (m, 9H), 1.78–1.83 (m, 6H). 13C
NMR (150 MHz, CDCl3): δ 191.8, 161.0, 158.1, 146.3, 138.3, 134.8,
127.7, 127.4, 127.0, 126.6, 122.3, 119.8, 119.1, 115.8, 113.8, 93.0,
55.5, 39.5 (3C), 36.3, 36.0 (3C), 28.0 (3C). ESI-HRMS (–): m/z [Mꢀ H]ꢀ
calculated for C27H28ClOꢀ4 451.1682 and 453.1652, found 451.1679 and
453.1655.
ESI-HRMS (–): m/z [Mꢀ H]ꢀ calculated for C32H30ClOꢀ3 497.1889 and
498.1923, found 497.1878 and 498.1917.
(E)-3-(3-adamantan-1-yl)-4-(benzyloxy)phenyl)-1-(2-hydroxy-5-
methoxyphenyl)prop-2-en-1-one (WA9). The reaction of 6d and 3b gave
WA9. Red solid; yield 61.8%; Mp: 113–116 ◦C. 1H NMR (600 MHz,
CDCl3): δ 12.54 (s, 1H), 7.92 (d, J = 15.3 Hz, 1H), 7.53 (s, 1H),
7.45–7.48 (m, 3H), 7.33–7.41 (m, 5H), 7.12 (dd, J = 3.0, 9.0 Hz, 1H),
6.93–6.96 (m, 2H), 5.14 (s, 2H), 3.81 (s, 3H), 2.06–2.16 (m, 9H),
1.71–1.77 (m, 6H). 13C NMR (150 MHz, CDCl3): δ 192.3, 159.3, 156.8,
150.6, 145.4, 138.1, 135.6, 127.6 (2C), 127.0, 126.9 (2C), 126.3 (2C),
126.1, 122.0, 118.9, 118.1, 116.2, 112.4, 111.8, 69.3, 55.1, 39.3 (3C),
36.1, 35.9 (3C), 27.9 (3C). ESI-HRMS (–): m/z [Mꢀ H]ꢀ calculated for
(E)-3-(3-(adamantan-1-yl)-4-(methoxymethoxy)phenyl)-1-(2-hy-
droxy-5-methoxyphenyl)prop-2-en-1-one (WA4). The reaction of 1-(2-
hydroxy-5-methoxyphenyl)ethanone 6d and 3a gave WA4. Yellow
solid; yield 50.4%; Mp: 110–112 ◦C. 1H NMR (600 MHz, CDCl3): δ 12.49
(s, 1H), 7.90 (d, J = 15.3 Hz, 1H), 7.53 (d, J = 2.3 Hz, 1H), 7.49 (dd, J =
2.3, 8.5 Hz, 1H), 7.45 (d, J = 15.3 Hz, 1H), 7.38 (d, J = 3.0 Hz, 1H), 7.13
(d, J = 8.5 Hz, 1H), 7.12 (dd, J = 3.0, 9.0 Hz, 1H), 6.96 (d, J = 9.0 Hz,
1H), 5.28 (s, 2H), 3.83 (s, 3H), 3.53 (s, 3H), 2.08–2.16 (m, 9H),
1.78–1.82 (m, 6H). 13C NMR (150 MHz, CDCl3): δ 193.4, 158.9, 157.8,
151.6, 146.4, 139.2, 128.2, 127.8, 127.7, 123.2, 119.9, 119.2, 117.6,
114.7, 113.4, 94.1, 56.5, 56.2, 40.5 (3C), 37.2, 37.0 (3C), 29.0 (3C). ESI-
HRMS (–): m/z [Mꢀ H]ꢀ calculated for C28H31O5ꢀ 447.2177, found
447.2177.
C
33H33Oꢀ4 493.2384, found 493.2384.
3-[(E)-3-(3-(adamantan-1-yl)-4-(benzyloxy)phenyl)acryloyl]-4-
hydroxybenzoic acid (WA10). The reaction of 6e and 3b gave WA10. Red
solid; yield 30.5%; Mp: 180–183 ◦C. 1H NMR (600 MHz, CDCl3): δ 8.60
(d, J = 2.0 Hz, 1H), 8.06 (dd, J = 2.0, 8.8 Hz, 1H), 7.91 (d, J = 15.3 Hz,
1H), 7.49–7.53 (m, 3H), 7.42–7.43 (m, 2H), 7.35 (t, J = 7.3 Hz, 2H),
7.29 (m, 1H), 6.97 (d, J = 8.4 Hz, 1H), 6.93 (d, J = 8.4 Hz, 1H), 5.13 (s,
2H), 2.00–2.11 (m, 9H), 1.65–1.69 (m, 6H). 13C NMR (150 MHz, CDCl3):
δ 192.5, 166.3, 165.3, 159.6, 146.6, 138.3, 135.7, 135.5, 131.1, 127.7,
127.6, 127.1, 127.0, 126.3, 125.9, 119.7, 118.6, 117.7, 115.5, 111.9,
69.4, 39.3 (2C), 36.2, 35.9 (2C), 27.9 (2C). ESI-HRMS (–): m/z [Mꢀ H]ꢀ
calculated for C33H31O5ꢀ 507.2177, found 507.2168.
(E)-3-[(3-adamantan-1-yl)-4-(methoxymethoxy)phenyl)acryloyl]-4-
hydroxybenzoic acid (WA5). The reaction of 3-acetyl-4-hydroxybenzoic
acid 6e and 3a gave WA5. Red solid; yield 40.5%; Mp: 202–205 ◦C.
1H NMR (600 MHz, DMSO‑d6): δ 8.57 (d, J = 2.2 Hz, 1H), 8.10 (d, J =
2.2, 8.6 Hz, 1H), 7.85 (d, J = 15.3 Hz, 1H), 7.80–7.82 (m, 2H), 7.64 (d, J
= 2.2 Hz, 1H), 7.15 (d, J = 8.6 Hz, 1H), 7.13 (d, J = 8.6 Hz, 1H), 5.38 (s,
2H), 3.50 (s, 3H), 2.10–2.16 (m, 9H), 1.79–1.83 (m, 6H). 13C NMR (150
MHz, DMSO‑d6): δ 193.2, 167.0, 164.4, 158.6, 146.1, 138.7, 136.4,
132.7, 128.8, 128.7, 127.8, 122.5, 122.2, 120.8, 118.3. 115.1, 94.2,
56.7, 40.4 (3C), 37.1, 36.9 (3C), 28.8 (3C). ESI-HRMS (–): m/z [Mꢀ H]ꢀ
calculated for C28H29O6ꢀ 461.1970, found 461.1974.
(E)-3-(5-(adamantan-1-yl)-2,4-bis(methoxymethoxy)phenyl)-1-(2-
hydroxyphenyl)prop-2-en-1-one (WA11). The reaction of 6a and 5-(ada-
mantan-1-yl)-2,4-bis(methoxymethoxy)-benzaldehyde (3c) gave WA11.
Yellow solid; yield 60.5%; Mp: 108–110 ◦C. 1H NMR (600 MHz, CDCl3):
δ 13.08 (s, 1H), 8.24 (d, J = 15.3 Hz, 1H), 7.93 (dd, J = 8.4, 1.5 Hz, 1H),
7.66 (d, J = 15.3 Hz, 1H), 7.52 (s, 1H), 7.46–7.52 (m, 1H), 7.26 (s, 1H),
7.02 (dd, J = 8.4, 1.5 Hz, 1H), 6.92–6.97 (m, 2H), 5.28 (s, 2H), 5.27 (s,
2H), 3.54 (s, 3H), 3.53 (s, 3H), 2.08–2.14 (m, 9H), 1.78–1.81 (m, 6H).
13C NMR (150 MHz, CDCl3): δ 193.2, 162.6, 158.8, 155.4, 140.6, 134.9,
131.8, 128.6, 126.6, 119.4, 117.6, 117.5, 117.0, 116.1, 100.8, 93.9,
93.3, 55.6, 55.5, 39.8 (3C), 36.0 (3C), 35.7, 28.0 (3C). ESI-HRMS (–): m/
z calculated for C29H33Oꢀ6 477.2283, found 477.2282.
(E)-3-(3-adamantan-1-yl)-4-(benzyloxy)phenyl)-1-(2-hydroxyphenyl)
prop-2-en-1-one (WA6). The reaction of 6a and 3-(adamant-1-yl)-4-
(benzyloxy)-benzaldehyde (3b) gave WA6. Red solid; yield 57.8%; Mp:
150–152 ◦C. 1H NMR (600 MHz, CDCl3): δ 12.91 (s, 1H), 7.85–7.88 (m,
2H), 7.51 (d, J = 2.2 Hz, 1H), 7.46 (d, J = 15.3 Hz, 1H), 7.42–7.43 (m,
4H), 7.35 (t, J = 7.5 Hz, 2H), 7.29 (d, J = 7.5 Hz, 1H), 6.95 (dd, J = 1.1,
8.4 Hz, 1H), 6.91 (d, J = 8.4 Hz, 1H), 6.88 (td, J = 7.5, 1.1 Hz, 1H), 5.11
(E)-3-(5-(adamantan-1-yl)-2,4-bis(methoxymethoxy)pheny)-1-(2-hy-
droxy-5-methylphenyl)prop-2-en-1-one (WA12). The reaction of 6b and
3c gave WA12. Yellow solid; yield 65.4%; Mp: 114–116 ◦C. 1H NMR
(600 MHz, DMSO‑d6): δ 12.88 (s, 1H), 8.21 (d, J = 15.6 Hz, 1H), 7.69 (d,
J = 2.0 Hz, 1H), 7.66 (d, J = 15.6 Hz, 1H), 7.51 (s, 1H), 7.28 (dd, J = 2.0,
8.4 Hz, 1H), 6.93 (s, 1H), 6.92 (d, J = 8.4 Hz, 1H), 5.27 (s, 2H), 5.26 (s,
2H), 3.53 (s, 6H), 2.35 (s, 3H), 2.08–2.15 (m, 9H), 1.78–1.81 (m, 6H).
13C NMR (150 MHz, CDCl3): δ 193.2, 160.4, 158.7, 155.3, 140.4, 135.9,
131.7, 128.3, 126.7, 126.6, 119.0, 117.2, 116.2, 100.8, 93.9, 93.2, 55.6,
55.5, 39.8 (3C), 36.0 (3C), 35.7, 28.0 (3C), 19.7. ESI-HRMS (–): m/z
[Mꢀ H]ꢀ calculated for C30H35Oꢀ6 491.2439, found 491.2430.
(s, 2H), 2.09–2.12 (m, 6H), 1.99–2.02 (m, 3H), 1.66–1.70 (m, 6H). 13
C
NMR (150 MHz, CDCl3): δ 193.7, 163.6, 160.4, 146.3, 139.1, 136.6,
136.0, 129.5, 128.6, 128.2, 127.8, 127.3, 126.7, 124.4, 121.9, 118.7,
117.2, 112.9, 70.3, 40.5 (3C), 37.2, 37.1 (3C), 29.0 (3C). ESI-HRMS (–):
m/z [Mꢀ H]ꢀ calculated for C32H31Oꢀ3 , 463.2279, found 463.2284.
(E)-3-(3-adamantan-1-yl)-4-(benzyloxy)phenyl)-1-(2-hydroxy-5-meth-
ylphenyl)prop-2-en-1-one (WA7). The reaction of 6b and 3b gave WA7.
Red solid; yield 42.8%; Mp: 101–103 ◦C. 1H NMR (600 MHz, CDCl3): δ
12.81 (s, 1H), 7.93 (d, J = 15.3 Hz, 1H), 7.68 (s, 1H), 7.48–7.55 (m, 5H),
7.39–7.44 (m, 2H), 7.37 (d, J = 8.0 Hz, 1H), 7.30 (d, J = 8.0 Hz, 1H),
6.98 (d, J = 8.5 Hz, 1H), 6.94 (d, J = 8.5 Hz, 1H), 5.17 (s, 2H), 2.36 (s,
3H), 2.07–2.17 (m, 9H), 1.72–1.76 (m, 6H). 13C NMR (150 MHz, CDCl3):
δ 192.6, 160.5, 159.3, 145.1, 138.2, 136.1, 135.6, 128.2, 127.6 (2C),
127.1, 127.0, 126.8, 126.7, 126.3 (2C), 126.2, 118.8, 117.3, 116.4,
111.9, 69.3, 39.4 (3C), 36.2, 36.0 (3C), 28.0 (3C), 19.7. ESI-HRMS (–):
m/z [Mꢀ H]ꢀ calculated for C33H33O–3 477.2435, found 477.2439.
(E)-3-(3-adamantan-1-yl)-4-(benzyloxy)phenyl)-1-(5-chloro-2-hydrox-
yphenyl)prop-2-en-1-one (WA8). The reaction of 6c and 3b gave WA8.
Yellow solid; yield 51.8%; Mp: 161–163 ◦C. 1H NMR (600 MHz, CDCl3):
δ 12.90 (s, 1H), 7.94 (d, J = 15.3 Hz, 1H), 7.86 (d, J = 2.5 Hz, 1H), 7.56
(d, J = 2.5 Hz, 1H), 7.52 (dd, J = 2.0, 8.5 Hz, 1H), 7.46–4.50 (m, 2H),
7.38–7.43 (m, 4H), 7.34–7.37 (m, 1H), 6.98 (d, J = 3.5 Hz, 1H), 6.96 (d,
(E)-3-(5-(adamantan-1-yl)-2,4-bis(methoxymethoxy)phenyl)-1-(5-
chloro-2-hydroxyphenyl)prop-2-en-1-one (WA13). The reaction of 6c and
3c gave WA13. Yellow solid; yield 63.4%; Mp: 140–143 ◦C. 1H NMR
(600 MHz, CDCl3): δ 13.00 (s, 1H), 8.24 (d, J = 15.6 Hz, 1H), 7.87 (d, J
= 2.5 Hz, 1H), 7.57 (d, J = 15.6 Hz, 1H), 7.50 (s, 1H), 7.41 (dd, J = 2.5,
9.0 Hz, 1H), 6.97 (d, J = 9.0 Hz, 1H), 6.94 (s, 1H), 5.29 (s, 2H), 5.27 (s,
2H), 3.55 (s, 3H), 3.54 (s, 3H), 2.10–2.13 (m, 9H), 1.78–1.82 (m, 6H).
13C NMR (150 MHz, CDCl3): δ 192.3, 161.0, 159.1, 155.6, 141.8, 134.6,
131.9, 127.8, 127.0, 122.2, 120.0, 119.1, 116.3, 115.8, 100.7, 93.9,
93.2, 55.6, 55.6, 39.8 (3C), 36.0 (3C), 35.7, 28.0 (3C). ESI-HRMS (–): m/
z [Mꢀ H]ꢀ calculated for C29H32ClOꢀ6 511.1893 and 513.1863, found
511.1880 and 513.1876.
(E)-3-(5-(adamantan-1-yl)-2,4-bis(methoxymethoxy)phenyl)-1-(2-hy-
droxy-5-methoxyphenyl)prop-2-en-1-one (WA14). The reaction of 6d and
3c gave WA14. Red solid; yield 53.2%; Mp: 114–116 ◦C. 1H NMR (600
MHz, CDCl3): δ 12.59 (s, 1H), 8.21 (d, J = 15.6 Hz, 1H), 7.63 (d, J =
15.6 Hz, 1H), 7.50 (s, 1H), 7.40 (d, J = 3.0 Hz, 1H), 7.11 (dd, J = 3.0,
9.0 Hz, 1H), 6.96 (d, J = 9.0 Hz, 1H), 6.94 (s, 1H), 5.28 (s, 2H), 5.27 (s,
2H), 3.83 (s, 3H), 3.53 (s, 3H), 3.53 (s, 3H), 2.07–2.14 (m, 9H),
J = 3.5 Hz, 1H), 5.18 (s, 2H), 2.08–2.17 (m, 9H), 1.71–1.78 (m, 6H). 13
C
NMR (150 MHz, CDCl3): δ 191.7, 161.0, 159.7, 146.4, 138.3, 135.5,
134.8, 127.7, 127.6 (2C), 127.3, 127.2, 127.0, 126.3 (2C), 125.9, 122.3,
119.8, 119.1, 115.5, 111.9, 69.4, 39.4 (3C), 36.2, 36.0 (3C), 28.0 (3C).
10