Page 5 of 8
The Journal of Organic Chemistry
4 Hz), 130.6, 133.8, 134.3; HRMS (ESI-TOF) m/z: [M + H]+
calcd for C16H9F6 315.0603; found: 315.0616.
131.8, 143.7, 143.9; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C18H17+ 233.1325; found: 233.1318.
+
1
2
3
4
5
6
7
8
9
2-Methoxyphenanthro[2,3-d][1,3]dioxole (3l): The title
compound was prepared following the general procedure
described above using 2b (0.2 mmol, 68.5 mg, 2.0 equiv.) and
1b (0.1 mmol, 21.3 mg, 1.0 equiv.). The product was isolated
2-Fluoro-9,10-dihydro-8H-cyclopenta[b]phenanthrene (3q):
The title compound was prepared following the general
procedure described above using 2c (0.2 mmol, 67.7 mg, 2.0
equiv.) and 1h (0.1 mmol, 20.1 mg, 1.0 equiv.). The product
was isolated in 78% yield (18.4 mg), white solid, mp 50-52, oC
eluent: hexane; 1H NMR (800 MHz, CDCl3): δ 2.21 (quin, J =
7.3 Hz, 2H), 3.11 (t, J = 7.3 Hz, 2H), 3.17 (t, J = 7.3 Hz, 2H),
7.30 (td, J = 8.3, 2.4 Hz, 1H), 7.62-7.74 (m, 2H), 7.71 (s, 1H),
7.82-7.86 (m, 1H), 8.26 (dd, J = 11.2, 2.3 Hz, 1H), 8.39(s, 1H);
13C{1H} NMR (200 MHz, CDCl3): δ 26.1, 32.7, 33.1, 107.5 (d,
J = 18 Hz), 114.9, 115.0, 117.8, 123.4, 125.2, 126.2, 128.5,
128.7 (d, J = 4 Hz), 130.4 (d, J = 8 Hz), 131.3, 131.9 (d, J = 8
Hz), 144.2 (d, J = 80 Hz), 161.4 (d, J = 24 Hz); HRMS (ESI-
TOF) m/z: [M + H]+ calcd for C17H14F+ 237.1075; found:
237.1065.
o
in 62% yield (15.6 mg), yellow solid, mp 136-137 C eluent:
1
hexane; H NMR (400 MHz, CDCl3): δ 4.01 (s, 3H), 6.10 (s,
2H), 7.17-7.22 (m, 2H), 7.49 (d, J = 8 Hz, 1H), 7.585 (d, J = 8
Hz, 1H), 7.75-7.82 (m, 2H), 7.93 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 55.4, 100.8, 101.3, 103.3, 105.7, 116.2, 124.1,
124.9, 125.7, 126.2, 128.8, 129.9, 131.3, 147.5, 147.7, 158.2;
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
+
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C16H13O3 253.0860;
found: 253.0878.
1-(Phenanthro[2,3-d][1,3]dioxol-2-yl)ethanone (3m): The
title compound was prepared following the general procedure
described above using 2b (0.2 mmol, 68.5 mg, 2.0 equiv.) and
1l (0.1 mmol, 24.1 mg, 1.0 equiv.). The product was isolated in
2-Chloro-9,10-dihydro-8H-cyclopenta[b]phenanthrene (3r):
The title compound was prepared following the general
procedure described above using 2c (0.2 mmol, 67.7 mg, 2.0
equiv.) and 1g (0.1 mmol, 21.7 mg, 1.0 equiv.). The product
was isolated in 62% yield (15.6 mg), yellow solid, mp 96-98 oC,
eluent: hexane; 1H NMR (800 MHz, CDCl3): δ 2.21 (quin, J =
7.4 Hz, 2H), 3.11 (t, J = 7.4 Hz, 2H), 3.16 (t, J = 7.4 Hz, 2H),
7.50 (dd, J = 8.4, 1.9 Hz, 1H), 7.61 (d, J = 8.8 Hz, 1H), 7.68 (d,
J = 8.8 Hz, 1H), 7.71 (s, 1H), 7.78 (d, J = 8.4 Hz, 1H), 8.44 (s,
1H), 8.61 (d, J = 1.4 Hz, 1H); 13C{1H} NMR (200 MHz,
CDCl3): δ 25.9, 32.6, 33.1, 117.6, 122.2, 123.4, 125.1, 126.4,
127.3, 128.3, 129.8, 130.1, 131.3, 131.5, 132.1, 144.3, 144.5;
HRMS (ESI-TOF) m/z: [M + H]+ calcd for C17H14Cl+ 253.0779;
found: 253.0789.
o
64% yield (18 mg), off white solid, mp 179-180 C eluent:
1
hexane; H NMR (400 MHz, CDCl3): δ 4.02 (s, 3H), 6.13 (s,
2H), 7.24 (s, 1H), 7.66 (d, J = 8 Hz, 1H), 7.72 (d, J = 8 Hz, 1H),
7.89 (d, J = 8 Hz, 1H), 8.11-8.15 (m, 2H), 9.22 (s, 1H); 13C{1H}
NMR (100 MHz, CDCl3): δ 52.3, 101.1, 101.5, 105.8, 124.7,
125.1, 125.5, 127.1, 127.5, 128.6, 128.7, 128.9, 129.4, 134.1,
147.9, 148.7, 167.4; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
+
C17H13O4 281.0809; found: 281.0828.
Phenanthro[2,3-d][1,3]dioxole-2-carbonitrile (3n): The title
compound was prepared following the general procedure
described above using 2b (0.2 mmol, 68.5 mg, 2.0 equiv.) and
1m (0.1 mmol, 20.8 mg, 1.0 equiv.). The product was isolated
in 59% yield (14.6 mg), yellow semi-solid, eluent: hexane; 1H
NMR (400 MHz, CDCl3): δ 6.15 (s, 2H), 7.25 (s, 1H), 7.63-7.70
(m, 2H), 7.76 (d, J = 8 Hz, 1H), 7.88-7.97 (m, 2H), 8.78 (s, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 100.7, 101.8, 105.9,
109.4, 119.6, 124.5, 125.8, 126.8, 128.1, 128.9, 129.5, 129.7,
133.5, 148.5, 149.1; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C16H10NO2+ 248.0707; found: 248.0702.
1,6,7-Trimethylphenanthrene (3s): The title compound was
prepared following the general procedure described above
using 2d (0.2 mmol, 65.3 mg, 2.0 equiv.) and 1e (0.1 mmol,
19.7 mg, 1.0 equiv.). The product was isolated in 74% yield
(16.3 mg), white solid, mp 112-114 oC, eluent: hexane; 1H NMR
(800 MHz, CDCl3): δ 2.51 (s, 3H), 2.57 (s, 3H), 2.79 (s, 3H),
7.45 (d, J = 8 Hz, 1H), 7.57 (t, J = 8 Hz, 1H), 7.69 (s, 1H), 7.74
(d, J = 8 Hz, 1H), 7.92 (d, J = 8 Hz, 1H), 8.50 (s, 1H), 8.61 (d,
J = 8 Hz, 1H); 13C{1H} NMR (200 MHz, CDCl3): δ 19.8, 19.9,
20.6, 120.6, 121.9, 123.2, 125.8, 126.1, 127.1, 128.5, 129, 130,
130.2, 130.5, 134.7, 135.7, 135.8; HRMS (ESI-TOF) m/z: [M
+ H]+ calcd for C17H17+ 221.1325; found: 221.1318.
9,10-Dihydro-8H-cyclopenta[b]phenanthrene (3o): The title
compound was prepared following the general procedure
described above using 2c (0.2 mmol, 67.7 mg, 2.0 equiv.) and
1a (0.1 mmol, 18.3 mg, 1.0 equiv.). The product was isolated in
79% yield (17 mg), yellow solid, mp 81-83 oC, eluent: hexane;
1H NMR (800 MHz, CDCl3): δ 2.21 (quin, J = 7.4 Hz, 2H), 3.12
(t, J = 7.4 Hz, 2H), 3.17 (t, J = 7.4 Hz, 2H), 7.54-7.58 (m, 1H),
7.61-7.64 (m, 1H), 7.66-7.71 (m, 2H), 7.72 (s, 1H), 7.88 (d, J
= 8 Hz, 1H), 8.55 (s, 1H), 8.67 (d, J = 8 Hz, 1H); 13C{1H} NMR
(200 MHz, CDCl3): δ 26.1, 32.6, 33.1, 117.6, 122.5, 123.3,
125.8, 125.9, 126.2, 127.1, 128.4, 129.2, 130.4, 131.1, 131.8,
143.7, 143.9; HRMS (ESI-TOF) m/z: [M + H]+ calcd for
C17H15+ 219.1169; found: 219.1165.
6-Chloro-2,3-dimethylphenanthrene (3t): The title compound
was prepared following the general procedure described above
using 2d (0.2 mmol, 65.3 mg, 2.0 equiv.) and 1g (0.1 mmol,
21.7 mg, 1.0 equiv.). The product was isolated in 77% yield
o
(18.5 mg), pale yellow solid, mp 80-82 C, eluent: hexane; 1H
NMR (800 MHz, CDCl3): δ 2.47 (s, 3H), 2.53 (s, 3H), 7.50 (dd,
J = 8.3, 2 Hz, 1H), 7.60-7.66 (m, 3H), 7.78 (d, J = 8.4 Hz, 1H),
8.33 (s, 1H), 8.59 (d, J = 1.5 Hz, 1H); 13C{1H} NMR (200 MHz,
CDCl3): δ 19.9, 20.5, 122.1, 122.9, 125.2, 126.4, 126.7, 127.6,
128.6, 129.8, 130.1, 130.7, 131.1, 132.2, 136.2, 136.6; HRMS
(ESI-TOF) m/z: [M + H]+ calcd for C16H14Cl+ 241.0779; found:
241.0789.
2,3-Difluorophenanthrene (3u):3n The title compound was
prepared following the general procedure described above
using 2e (0.2 mmol, 66.8 mg, 2.0 equiv.) and 1a (0.1 mmol,
18.3 mg, 1.0 equiv.). The product was isolated in 52% yield (11
mg), white solid, eluent: hexane.
2-Methyl-9,10-dihydro-8H-cyclopenta[b]phenanthrene (3p):
The title compound was prepared following the general
procedure described above using 2c (0.2 mmol, 67.7 mg, 2.0
equiv.) and 1d (0.1 mmol, 19.7 mg, 1.0 equiv.). The product
was isolated in 63% yield (14.6 mg), yellow solid, mp 90-92 oC,
eluent: hexane; 1H NMR (800 MHz, CDCl3): δ 2.20 (quin, J =
7.3 Hz, 2H), 2.62 (s, 3H), 3.11 (t, J = 7.3 Hz, 2H), 3.17 (t, J =
7.3 Hz, 2H), 7.39 (d, J = 7.9 Hz, 1H), 7.62 (s, 2H), 7.70 (s, 1H),
7.76 (d, J = 7.9 Hz, 1H), 8.46 (s, 1H), 8.53(s, 1H); 13C{1H}
NMR (200 MHz, CDCl3): δ 26.1, 32.6, 33.1, 117.6, 122.5,
123.3, 125.7, 125.9, 126.1, 127.0, 128.4, 129.2, 130.4, 131.1,
6,7-Difluoro-1-methylphenanthrene (3v): The title compound
was prepared following the general procedure described above
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