Rh-Catalyzed Coupling of Aroyl Chlorides with Alkenes
FULL PAPERS
6b,7,8,9,10,10a-Hexahydro-7,10-methanofluoranthene
Typical Experimental Procedure for the Reaction of 1
with Cyclic Alkenes
1
(13a):[16] mp 52–548C; H NMR (CDCl3, 400 MHz): d¼0.70
(d, 1H, J¼10.3 Hz), 0.87 (d, 1H, J¼10.3 Hz), 1.42–1.47 (m,
2H), 1.59–1.64 (m, 2H), 2.32–2.33 (m, 2H), 3.39 (s, 2H), 7.17
(d, 2H, J¼7.0 Hz), 7.37 (dd, 2H, J¼7.0, 8.3 Hz), 7.50 (d, 2H,
J¼8.1 Hz); 13C NMR (CDCl3, 100 MHz): d¼29.36, 32.64,
42.85, 53.46, 119.00, 122.37, 127.90, 131.03, 140.82, 148.29;
MS: m/z¼220 (Mþ).
A mixture of 1a (1 mmol, 141 mg), 9a (5 mmol, 470 mg), and
[RhCl(C2H4)2]2 (0.01 mmol, 4 mg) in refluxing o-xylene
(5 mL) was stirred under N2 (1 atm). After 20 h, the mixture
was cooled to room temperature. After evaporation of the sol-
vents under vacuum, the product 1,2,3,4,4a,9a–hexahydro-1,4-
methanofluoren-9-one (10a)[17] was isolated by column chro-
matography on silica gel using hexane-ethyl acetate as eluent;
yield: 166 mg (84%); mp 51–538C; 1H NMR (CDCl3,
400 MHz): d¼0.80 (dt, 1H, J¼10.5, 1.8 Hz), 0.95 (dt, 1H, J¼
10.5, 1.5 Hz), 1.35–1.50 (m, 2H), 1.60–1.76 (m, 2H), 2.41 (d,
1H, J¼4.0 Hz), 2.50 (d, 1H, J¼6.2 Hz), 2.60 (d, 1H, J¼
4.0 Hz), 3.15 (d, 1H, J¼5.8 Hz), 7.35 (t, 1H, J¼7.6 Hz), 7.50
(dd, 1H, J¼0.7, 7.6 Hz), 7.61 (dt, 1H, J¼1.1, 7.6 Hz), 7.71 (d,
1H, J¼7.6 Hz); 13C NMR (CDCl3, 100 MHz): d¼28.65,
28.86, 32.18, 40.36, 41.24, 48.01, 55.81, 123.14, 126.12, 127.35,
134.91, 139.04, 157.21, 208.85; MS: m/z¼198 (Mþ); anal. calcd.
for C14H14O: C 84.81, H 7.12; found: C 84.52, H, 7.25.
1,2,3,4,4a,9a-Hexahydro-7-methyl-1,4-methanofluoren-9-
one (10b): mp 74–768C; 1H NMR (CDCl3, 400 MHz): d¼0.80
(dt, 1H, J¼10.5, 1.5 Hz), 0.93 (dt, 1H, J¼10.5, 1.5 Hz), 1.33–
1.48 (m, 2H), 1.59–1.75 (m, 2H), 2.37–2.40 (m, 4H), 2.49 (d,
1H, J¼5.8 Hz), 2.58 (d, 1H, J¼4.4 Hz), 3.10 (d, 1H, J¼
6.2 Hz), 7.37–7.44 (m, 2H), 7.51 (s, 1H); 13C NMR (CDCl3,
100 MHz): d¼21.06, 28.65, 28.82, 32.12, 40.28, 41.17, 47.66,
56.17, 123.07, 125.77, 136.20, 137.29, 139.21, 154.66, 208.94;
MS: m/z¼212 (Mþ); anal. calcd. for C15H16O: C 84.87, H
7.60; found: C 84.61, H 7.59.
7-Bromo-1,2,3,4,4a,9a–hexahydro-1,4-methanofluoren-9-
one (10e): mp 84–858C; 1H NMR (CDCl3, 400 MHz): d¼0.80
(dt, 1H, J¼10.5, 1.8 Hz), 0.97 (dt, 1H, J¼10.5, 1.5 Hz), 1.33–
1.49 (m, 2H), 1.60–1.77 (m, 2H), 2.39 (d, 1H, J¼4.4 Hz), 2.52
(d, 1H, J¼5.9 Hz), 2.60 (d, 1H, J¼4.4 Hz), 3.10 (d, 1H, J¼
6.2 Hz), 7.38 (d, 1H, J¼8.1 Hz), 7.70 (dd, 1H, J¼1.8, 8.1 Hz),
7.83 (d, 1H, J¼1.8 Hz); 13C NMR (CDCl3, 100 MHz): d¼
28.55, 28.81, 32.24, 40.52, 41.17, 47.73, 56.19, 121.74, 126.17,
127.72, 137.68, 140.90, 155.69, 207.25; MS: m/z¼276, 278
(Mþ); anal. calcd. for C14H13BrO: C 60.67, H 4.73, Br 28.83;
found: C 60.38, H 4.74, Br 28.77.
1,2,3,4,4a,9a-Hexahydro-5-methyl-1,4-methanofluoren-9-
one (10k): mp 68–728C; 1H NMR (CDCl3, 400 MHz): d¼0.84
(dt, 1H, J¼10.6, 1.8 Hz), 0.95 (dt, 1H, J¼10.6, 1.5 Hz), 1.35–
1.51 (m, 2H), 1.61–1.77 (m, 2H), 2.45 (s, 3H), 2.50 (d, 2H, J¼
5.1 Hz), 2.63 (d, 1H, J¼4.0 Hz), 3.12 (d, 1H, J¼5.9 Hz), 7.27
(t, 1H, J¼7.7 Hz), 7.41 (d, 1H, J¼7.7 Hz), 7.56 (d, 1H, J¼
7.7 Hz); 13C NMR (CDCl3, 100 MHz): d¼18.05, 28.43, 29.19,
32.29, 38.92, 40.26, 47.26, 56.06, 120.71, 127.62, 135.78, 135.81,
139.06, 155.39, 209.22; MS: m/z¼212 (Mþ); anal. calcd. for
C15H16O: C 84.87, H 7.60; found: C 84.59, H 7.56.
8-Ethylidene-6b,7,8,9,10,10a–hexahydro-7,10-methano-
fluoranthene (13b, major:minor¼ca. 3:1): oil; 1H NMR
(CDCl3, 400 MHz): d¼0.84 (d, 1H, J¼10.3 Hz), 1.08 (d, 1H,
J¼10.3 Hz), 1.62 (d, 3H, J¼6.6 Hz, major), 1.81 (d, 3H, J¼
6.6 Hz, minor), 2.11–2.36 (m, 2H), 2.48–2.49 (m, 1H, minor),
2.54–2.56 (m, 1H, major), 2.79 (s, 1H, major), 3.11 (s, 1H, mi-
nor), 3.53–3.60 (m, 2H), 5.20–5.25 (m, 1H, minor), 5.48–
5.54 (m, 1H, major), 7.27–7.29 (m, 2H), 7.46 (dd, 2H, J¼7.0,
8.3 Hz), 7.59 (d, 2H, J¼8.3 Hz); 13C NMR (CDCl3,
100 MHz): d¼14.03, 14.63, 33.01, 33.28, 35.30, 38.29, 43.00,
43.02, 45.56, 51.06, 52.59, 52.76, 52.92, 53.44, 112.78, 113.40,
119.09, 119.13, 119.17, 119.21, 122.52, 122.56, 122.62, 127.93,
127.97, 131.08, 140.95, 144.30, 145.19, 146.96, 147.07, 147.92,
147.96; MS: m/z¼246 (Mþ); anal. calcd. for C19H18: C 92.64,
H 7.36; found: C 92.36, H 7.48.
1-Phenylacenaphthylene (15a): mp 52–548C (ref.[25] 56–
1
588C); H NMR (CDCl3, 400 MHz): d¼7.17 (s, 1H), 7.38 (t,
1H, J¼7.3 Hz), 7.49 (t, 2H, J¼7.3 Hz), 7.55 (dd, 1H, J¼6.9,
8.3 Hz), 7.60 (dd, 1H, J¼6.9, 8.3 Hz), 7.69 (d, 1H, J¼6.9 Hz),
7.78–7.81 (m, 3H), 7.85 (d, 1H, J¼8.3 Hz), 7.94 (d, 1H, J¼
6.9 Hz); 13C NMR (CDCl3, 100 MHz): d¼123.86, 124.42,
125.54, 127.00, 127.49, 127.58, 127.61, 127.93 (overlapped),
128.41, 128.76, 129.32, 136.17, 138.66, 139.11, 143.46; MS: m/
z¼228 (Mþ).
1-(4-Methylphenyl)acenaphthylene (15b): mp 64–668C;
1H NMR (CDCl3, 400 MHz): d¼2.43 (s, 3H), 7.13 (s, 1H),
7.30 (d, 2H, J¼8.1 Hz), 7.54 (dd, 1H, J¼7.0, 8.1 Hz), 7.59
(dd, 1H, J¼7.0, 8.1 Hz), 7.66 (d, 1H, J¼7.0 Hz), 7.69 (d, 2H,
J¼8.1 Hz), 7.78 (d, 1H, J¼8.4 Hz), 7.84 (d, 1H, J¼8.1 Hz),
7.93 (d, 1H, J¼7.0 Hz); 13C NMR (CDCl3, 100 MHz): d¼
21.29, 123.61, 124.37, 124.91, 126.80, 127.46, 127.50, 127.80,
127.92, 128.38, 129.35, 129.49, 133.31, 137.49, 138.82, 139.25,
143.43; MS: m/z¼242 (Mþ); anal. calcd. for C19H14: C 94.18,
H 5.82; found: C 93.90, H 5.95.
1-(4-Methoxyphenyl)acenaphthylene (15d): mp 69–718C
1
(ref.[26] 76.5–77.58C); H NMR (CDCl3, 400 MHz): d¼3.88
(s, 3H), 7.03 (d, 2H, J¼8.8 Hz), 7.08 (s, 1H), 7.53 (dd, 1H,
J¼7.0, 8.1 Hz), 7.59 (dd, 1H, J¼7.0, 8.1 Hz), 7.64 (d, 1H, J¼
6.6 Hz), 7.73 (d, 2H, J¼8.8 Hz), 7.77 (d, 1H, J¼8.1 Hz), 7.84
(d, 1H, J¼8.1 Hz), 7.92 (d, 1H, J¼7.0 Hz); 13C NMR
(CDCl3, 100 MHz): d¼76.69, 114.27, 123.40, 124.19, 124.28,
126.62, 127.42, 127.50, 127.95, 128.37, 128.85, 129.06, 129.34,
138.91, 139.35, 143.09, 159.37; MS: m/z¼258 (Mþ); anal. calcd
for C19H14O: C 88.34, H 5.46; found: C 88.01, H, 5.59.
3a,4,5,6,7,7a-Hexahydro-2-phenyl-4,7-methano-1H-inden-
1-one (12): mp 95–978C (ref.[24] 958C); 1H NMR (CDCl3,
400 MHz): d¼1.00 (dt, 1H, J¼10.5, 1.5 Hz), 1.12 (dt, 1H, J¼
10.5, 2.2 Hz), 1.29–1.40 (m, 2H), 1.58–1.76 (m, 2H), 2.28 (d,
1H, J¼4.4 Hz), 2.37 (d, 1H, J¼5.4 Hz), 2.50 (d, 1H, J¼
4.4 Hz), 2.69–2.71 (m, 1H), 7.30–7.40 (m, 3H), 7.64 (d, 1H,
J¼3.3 Hz), 7.68–7.70 (m, 2H); 13C NMR (CDCl3, 100 MHz):
d¼28.39, 29.15, 31.28, 38.36, 39.46, 47.73, 54.94, 127.04,
128.37, 128.39, 131.52, 146.12, 160.15, 208.98; MS: m/z¼224
(Mþ); anal. calcd. for C16H16O: C 85.68, H 7.19; found: C
85.48, H 7.19.
1-(4-Nitrophenyl)acenaphthylene (15g): mp 130–1318C;
1H NMR (CDCl3, 400 MHz): d¼7.35 (s, 1H), 7.61 (dd, 1H,
J¼7.0, 8.1 Hz), 7.64 (dd, 1H, J¼7.0, 8.1 Hz), 7.78 (d, 1H, J¼
7.0 Hz), 7.88–7.95 (m, 5H), 8.33 (d, 2H, J¼9.2 Hz);
13C NMR (CDCl3, 100 MHz): d¼124.16, 124.53, 125.17,
127.66, 128.20 (overlapped), 128.23, 128.27, 128.49, 128.58,
129.30, 137.56, 138.30, 140.90, 142.76, 146.89; MS: m/z¼273
(Mþ); anal. calcd. for C18H11NO2: C 79.11, H 4.06, N 5.13;
found: C 79.38, H 4.18, N 5.02.
Adv. Synth. Catal. 2004, 346, 1765–1772
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1771