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Synthesis of the
Dimer of 10-Methylene-9-phenanthrones 1a-g - General Procedure
To
a stirred suspension of the 9-phenanthrol (1 mmol) in MeOH (10mL, 9d was in THF-MeOH = 4:1), l-proline (6 mg, 0.05 mmol) and 36% aq
formaldehyde (0.1 mL, 1.2 mmol) were added. The mixture was stirred
at r.t. for 2-4 h. The reaction product was evaporated
under vacuum. The residue was purified by flash column chromatography
on SiO2, eluting with PE-EtOAc, to produce the
dimer of 10-methylene-9-phenanthrones.
<A NAME="RW00209ST-10">10</A>
Selective Spectroscopic
Data of the Dimer of 10-Methylene-9-phenanthrones
Compound 1a: ¹H NMR (300 MHz,
CDCl3): δ = 2.29 (m, 1 H), 2.54-2.60
(m, 2 H), 2.92 (m, 1 H), 3.72 (s, 3 H), 3.74 (s, 3 H), 3.77 (s,
3 H), 3.87 (s, 3 H), 3.89 (s, 3 H), 3.91 (s, 3 H), 3.96 (s, 6 H),
4.00 (s, 3 H), 4.02 (s, 3 H), 4.03 (s, 3 H), 4.06 (s, 3 H), 6.83
(s, 1 H), 7.11 (s, 1 H), 7.26 (s, 1 H), 7.68 (s, 1 H). ¹³C
NMR (75 MHz, CDCl3): δ = 20.6, 32.8,
55.9, 55.9, 56.1, 56.3, 61.0, 61.1, 61.1, 61.2, 61.2, 61.3, 61.4,
61.5, 83.1, 97.4, 98.0, 103.6, 105.2, 107.7, 113.1, 116.3, 117.7,
121.5, 123.1, 124.9, 132.4, 140.3, 142.3, 142.5, 146.7, 151.7, 151.8,
152.0, 152.2, 152.3, 152.4, 153.2, 153.6, 197.6. HRMS-FAB: m/z [M + H]+ calcd
for C42H44O14: 773.2809; found:
773.2810. Anal. Calcd for C42H44O14:
C, 65.28; H, 5.74; O, 28.98. Found: C, 65.41; H, 5.72; O, 28.92.
Compound 1b: ¹H NMR (300 MHz,
CDCl3): δ = 2.27 (m, 1 H), 2.51 (m,
1 H), 2.82 (m, 1 H), 3.04 (m, 1 H), 3.83 (s, 3 H), 3.93 (s, 3 H),
3.96 (s, 3 H), 3.99 (s, 3 H), 4.00 (s, 3 H), 4.04 (s, 3 H), 4.10
(s, 3 H), 4.11 (s, 3 H), 4.14 (s, 3 H), 7.14 (s, 1 H), 7.24 (s,
1 H), 7.29 (s, 1 H), 7.36 (s, 1 H), 7.42 (s, 1 H), 7.52 (s, 1 H),
7.83 (m, 3 H). ¹³C NMR (75 MHz, CDCl3):
δ = 19.6,
34.1, 55.8, 55.8, 56.0, 56.1, 56.2, 56.2, 56.3, 56.5, 82.3, 102.5,
103.1, 103.3, 103.9, 104.7, 106.9, 107.4, 108.7, 109.2, 119.7, 119.9,
121.5, 122.5, 124.6, 126.1, 131.6, 133.8, 146.6, 147.1, 148.7, 148.9,
149.0, 149.1, 149.2, 149.9, 154.5, 198.1. HRMS-FAB: m/z [M + H]+ calcd
for C38H36O10: 653.2387; found:
653.2389. Anal. Calcd for C38H36O10:
C, 69.93; H, 5.56; O, 24.51. Found: C, 69.77; H, 5.50; O, 24.60.
Compound 1c: ¹H NMR (300 MHz,
CDCl3): δ = 2.27 (m, 1 H), 2.54 (m,
1 H), 2.60 (m, 1 H), 2.91 (m, 1 H), 3.89 (s, 3 H), 3.94 (s, 3 H),
3.99 (s, 3 H), 4.02 (s, 3 H), 6.03 (d, 2 H), 6.14 (d, 2 H), 6.17
(d, 2 H), 6.21 (d, 2 H), 6.80 (s, 1 H), 7.12 (s, 1 H), 7.17 (s,
1 H), 7.70 (s, 1 H). ¹³C NMR (75 MHz,
CDCl3): δ = 20.9, 33.9, 56.2, 56.3,
56.6, 56.7, 83.3, 97.4, 98.0, 101.2, 101.3, 101.8, 102.4, 102.8,
103.8, 106.1, 108.1, 115.1, 116.2, 117.9, 122.1, 123.4, 125.2, 132.6,
141.3, 142.3, 142.6, 145.0, 151.6, 151.8, 152.0, 152.2, 152.4, 152.5, 153.6,
154.2, 197.0. HRMS-FAB: m/z [M + H]+ calcd
for C38H28O14: 709.1557; found:
709.1554. Anal. Calcd for C38H28O14:
C, 64.41; H, 3.98; O, 31.61. Found: C, 64.19; H, 3.41; O, 31.55.
Compound 1d: ¹H NMR (300 MHz,
DMSO-d
6): δ = 2.24
(m, 1 H), 2.33 (m, 1 H), 2.68 (m, 1 H), 3.42 (m, 1 H), 5.92 (s,
1 H), 6.06 (s, 2 H), 6.08 (s, 1 H), 6.09 (s, 1 H), 6.10 (s, 1 H), 6.19
(s, 1 H), 6.24 (s, 1 H), 7.02 (d, 1 H), 7.12 (d, 1 H), 7.26 (d,
1 H), 7.28 (d, 1 H), 7.55 (d, 1 H), 7.58 (d, 1 H), 8.16 (s, 1 H),
8.19 (s, 1 H). ¹³C NMR (75 MHz, DMSO-d
6): δ = 20.0, 28.9,
80.2, 100.6, 101.1, 101.6, 108.8, 109.4, 111.8, 113.8, 116.4, 117.1,
117.4, 118.1, 120.0, 122.1, 124.1, 126.2, 129.7, 141.9, 144.9, 145.3,
145.7, 146.6, 147.9, 148.2, 193.7. HRMS-FAB: m/z [M + H]+ calcd
for C34H20O10: 589.1135; found:
589.1136. Anal. Calcd for C34H20O10:
C, 69.39; H, 3.43; O, 27.19. Found: C, 69.54; H, 3.52; O, 27.05.
Compound 1e: ¹H NMR (300 MHz,
CDCl3): δ = 2.22 (m, 1 H), 2.46 (s,
3 H), 2.49 (m, 1 H), 2.52 (s, 3 H), 2.58 (s, 3 H), 2.63 (s, 3 H),
2.76 (m, 1 H), 3.01 (m, 1 H), 7.22 (m, 2 H), 7.38 (d, 1 H), 7.45
(d, 1 H), 7.65-7.83 (m, 5 H), 8.38 (m, 3 H). ¹³C
NMR (75 MHz, CDCl3): δ = 19.3, 21.4,
22.1, 22.2, 22.3, 34.0, 83.2, 108.5, 122.2, 122.4, 122.8, 123.6,
124.0, 125.0, 126.0, 126.3, 126.8, 127.9, 128.1, 128.3, 129.4, 129.9,
130.1, 133.0, 136.0, 136.8, 137.2, 137.7, 138.2, 145.3, 198.1.
HRMS-FAB: m/z [M + H]+ calcd
for C34H28O2: 469.2168; found:
469.2165. Anal. Calcd for C34H28O2:
C, 87.15; H, 6.02; O, 6.83. Found: C, 87.06; H, 5.98; O, 6.79.
Compound 1f: ¹H NMR (300 MHz,
CDCl3): δ = 2.28 (td, 1 H), 2.55 (d,
1 H), 2.80 (td, 1 H), 3.09 (d, 1 H), 7.25-7.89 (m, 13 H),
8.52 (d, 1 H), 8.68 (t, 2 H). ¹³C NMR
(75 MHz, CDCl3): δ = 19.5, 33.8, 83.2,
108.5, 122.4, 122.5, 123.0, 123.3, 124.0, 124.6, 126.0, 126.7, 128.8,
129.6, 130.1, 130.7, 132.0, 134.8, 136.9, 140.1, 148.0, 198.6. HRMS-FAB: m/z [M + H]+ calcd
for C30H20O2: 413.1542; found: 413.1544.
Anal. Calcd for C30H20O2: C, 87.36;
H, 4.89; O, 7.76. Found: C, 86.92; H, 4.88; O, 7.73.
Compound 1g: ¹H NMR (300 MHz,
CDCl3): δ = 2.26 (m, 1 H), 2.50 (m,
1 H), 2.76 (m, 1 H), 3.01 (m, 1 H), 7.17 (m, 2 H), 7.37 (m, 2 H),
7.55 (m, 2 H), 7.74-7.85 (m, 2 H), 7.97 (m, 1 H), 8.15
(m, 2 H), 8.44 (m, 1 H). ¹³C NMR (75
MHz, CDCl3): δ = 19.4, 33.9, 82.6,
102.2, 107.4, 107.9, 108.3, 108.6, 110.3, 110.6, 110.7, 111.5, 111.8,
115.8, 116.0, 116.2, 116.4, 116.7, 117.1, 117.4, 124.5, 124.6, 125.0, 125.1,
128.2, 128.3, 131.0, 131.1, 196.3. HRMS-FAB: m/z [M + H]+ calcd
for C30H16F4O2: 485.1165;
found: 485.1169. Anal. Calcd for C30H16F4O2:
C, 74.38; H, 3.33; F, 15.69; O, 6.61. Found: C, 74.55; H, 3.39;
F, 15.58; O, 6.66.
