The Journal of Organic Chemistry
Note
(
1Z,3E)-1-(2-Benzoyl-1H-inden-1-ylidene)-1,4-diphenylbut-3-en-
(400 MHz, CDCl ) δ 7.96 (d, J = 8.00 Hz, 2H), 7.60 (d, J = 8.00 Hz,
3
1
2
-one (2j). Yield 64 mg, 49%; light-yellow solid; mp 86−87 °C; H
1H), 7.54−7.48 (m, 5H), 7.46−7.43 (m, 2H), 7.27−7.26 (m, 1H),
NMR (400 MHz, CDCl ) δ 7.93 (d, J = 8.00 Hz, 2H), 7.54−7.47 (m,
7.13 (s, 1H), 6.89 (d, J = 8.00 Hz, 1H), 6.32 (d, J = 8.00 Hz, 1H), 2.23
3
(s, 3H); 13C NMR (100 MHz, CDCl ) δ 203.1, 193.4, 163.2 (d, J =
1
6
7
6
1
1
1
+
H), 7.44−7.40 (m, 2H), 7.36−7.34 (m, 2H), 7.31−7.27 (m, 4H),
3
.23−7.19 (m, 3H), 6.97−6.94 (m, 1H), 6.72 (d, J = 16.00 Hz, 1H),
247 Hz), 149.0, 148.3, 142.6, 138.0, 137.9, 135.8, 135.7, 135.2, 134.7,
1
3
2
.56 (d, J = 8.00 Hz, 1H); C NMR (100 MHz, CDCl ) δ 193.5,
129.7, 129.5, 129.0, 128.4, 125.5, 123.5, 110.3 (d, J = 22 Hz), 110.2
3
2
+
93.0, 146.9, 143.9, 141.9, 141.2, 140.2, 139.4, 138.3, 137.1, 136.3,
34.6, 132.7, 130.4, 129.7, 129.7, 129.4, 129.3, 129.0, 128.6, 128.5,
28.2, 127.8, 125.8, 124.8, 123.2; HRMS (ESI) calcd for C H O [M
(d, J = 23 Hz), 29.4; HRMS (ESI) calcd for C H FO [M + Na]
25 17 2
391.1105, found 391.1114.
32
22
2
(Z)-1-(2-Benzoyl-5-chloro-1H-inden-1-ylidene)-1-phenylpropan-
+
1
Na] 461.1512, found 461.1498.
Z)-1-(2-Benzoyl-1H-inden-1-ylidene)-1-phenylpropan-2-one
2-one (2r). Yield 75 mg, 65%; yellow solid; mp 80−81 °C; H NMR
(
(400 MHz, CDCl ) δ 7.94 (d, J = 8.00 Hz, 2H), 7.60 (d, J = 8.00 Hz,
3
1
(
(
7
6
2k). Yield 90 mg, 86%; light-yellow solid; mp 66−67 °C; H NMR
1H), 7.54−7.48 (m, 5H), 7.47−7.44 (m, 2H), 7.13 (s, 1H), 6.70−6.97
1
3
400 MHz, CDCl ) δ 7.96 (d, J = 8.00 Hz, 2H), 7.61−7.48 (m, 8H),
(m, 1H), 6.64−6.59 (m, 1H), 6.37−6.34 (m, 1H), 2.23 (s, 3H);
C
3
.29 (d, J = 8.00 Hz, 1H), 7.21−7.17 (m, 2H), 6.95−6.91 (m, 1H),
NMR (100 MHz, CDCl ) δ 203.1, 193.4, 149.0, 142.6, 141.0, 140.5,
3
1
3
.42 (d, J = 8.00 Hz, 1H), 2.24 (s, 3H); C NMR (100 MHz, CDCl )
137.9, 136.1, 135.7, 135.2, 134.7, 133.1, 129.7, 129.6, 129.5, 128.9,
3
δ 203.3, 193.7, 148.3, 142.6, 141.1, 139.7, 138.3, 137.2, 137.0, 136.1,
32.8, 129.7, 129.4, 129.0, 128.9, 128.4, 127.9, 124.7, 123.3, 29.5;
128.4, 127.5, 125.5, 29.4; HRMS (ESI) calcd for C H ClO [M +
Na] 407.0809, found 407.0780.
25
17
2
+
1
+
HRMS (ESI) calcd for C H O [M + Na] 373.1199, found
(Z)-2-(2-Benzoyl-1H-inden-1-ylidene)-2-(4-methoxyphenyl)-1-
25
18
2
373.1188.
phenylethanone (2s). Yield 101 mg, 76%; yellow solid; mp 181−182
1
(
Z)-1-(2-Benzoyl-1H-inden-1-ylidene)-1-phenylbutan-2-one (2l).
°C; H NMR (400 MHz, CDCl ) δ 7.82 (d, J = 8.00 Hz, 2H), 7.76 (d,
3
1
Yield 93 mg, 85%; light-yellow solid; mp 67−68 °C; H NMR (400
J = 8.00 Hz, 2H), 7.52−7.49 (m, 1H), 7.44−7.33 (m, 6H), 7.30−7.22
MHz, CDCl ) δ 7.97 (d, J = 8.00 Hz, 2H), 7.61−7.57 (m, 1H), 7.51−
(m, 3H), 7.18 (s, 1H), 7.05−7.01 (m, 1H), 6.93 (d, J = 8.00 Hz, 2H),
3
6.88 (d, J = 8.00 Hz, 1H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl
)
3
7
6
0
1
1
.45 (m, 7H), 7.29 (d, J = 8.00 Hz, 1H), 7.19−7.16 (m, 2H), 6.94−
.90 (m, 1H), 6.40 (d, J = 8.00 Hz, 1H), 2.62−2.57 (m, 2H), 0.99−
δ 196.0, 193.2, 160.3, 146.7, 141.9, 140.9, 139.6, 138.8, 138.2, 137.5,
1
3
.95 (m, 3H); C NMR (100 MHz, CDCl ) δ 206.2, 193.5, 148.5,
137.2, 132.5, 132.4, 131.3, 130.2, 129.6, 129.1, 128.8, 128.1, 127.9,
3
124.6, 123.3, 114.5, 55.3; HRMS (ESI) calcd for C31H O
[M + Na]+
42.1, 141.1, 139.8, 138.3, 137.1, 137.1, 136.5, 132.8, 129.7, 129.3,
29.2, 129.0, 128.7, 128.3, 127.8, 124.6, 123.2, 35.2, 7.4; HRMS (ESI)
calcd for C H O [M + Na] 387.1361, found 387.1370.
22 3
465.1461, found 465.1463.
+
(Z)-2-(2-Benzoyl-1H-inden-1-ylidene)-2-(4-chlorophenyl)-1-phe-
26
20
2
(
Z)-1-(2-Benzoyl-1H-inden-1-ylidene)-1,3-diphenylpropan-2-one
nylethanone (2t). Yield 106 mg, 79%; yellow solid; mp 197−198 °C;
1
1
(
2m). Yield 87 mg, 68%; yellow solid; mp 101−102 °C; H NMR (400
H NMR (400 MHz, CDCl ) δ 7.83 (d, J = 8.00 Hz, 2H), 7.74 (d, J =
3
MHz, CDCl ) δ 7.98 (d, J = 8.00 Hz, 2H), 7.61−7.57 (m, 1H), 7.50−
8.00 Hz, 2H), 7.53−7.46 (m, 6H), 7.40−7.34 (m, 3H), 7.31−7.25 (m,
3
3H), 7.20 (s, 1H), 7.07 (m, 1H), 6.74 (d, J = 8.00 Hz, 1H); 13C NMR
7
7
8
1
1
1
4
.48 (m, 5H), 7.39−7.37 (m, 2H), 7.29 (d, J = 8.00 Hz, 1H), 7.21−
.13 (m, 5H), 7.02−7.00 (m, 2H), 6.94−6.91 (m, 1H), 6.45 (d, J =
(100 MHz, CDCl ) δ 195.2, 192.8, 145.0, 142.5, 141.0, 139.4, 139.4,
3
1
3
.00 Hz, 1H), 3.95 (s, 2H); C NMR (100 MHz, CDCl ) δ 202.5,
138.0, 137.2, 136.8, 135.4, 135.3, 132.7, 132.6, 131.0, 130.1, 129.5,
3
93.5, 148.3, 142.4, 141.1, 139.6, 138.2, 137.6, 137.1, 135.8, 134.2,
32.8, 129.9, 129.8, 129.3, 129.3, 128.9, 128.8, 128.4, 128.0, 127.9,
26.4, 124.7, 123.3, 48.2; HRMS (ESI) calcd for C H O [M + Na]
129.4, 129.2, 128.2, 128.1, 128.1, 124.7, 123.5; HRMS (ESI) calcd for
+
C H ClO [M + Na] 469.0966, found 469.0974.
30
19
2
+
31
22
2
(Z)-1-(1-(2-Oxo-1,2-diphenylethylidene)-1H-inden-2-yl)pentan-1-
1
49.1517, found 449.1528.
Z)-2-(2-Benzoyl-1H-inden-1-ylidene)-1-cyclohexyl-2-phenyletha-
one (2w). Yield 86 mg, 73%; yellow solid; mp 133−134 °C; H NMR
(400 MHz, CDCl ) δ 7.91 (d, J = 8.00 Hz, 2H), 7.53 (s, 1H), 7.46−
(
3
1
none (2n). Yield 56 mg, 45%; yellow solid; mp 102−103 °C; H NMR
400 MHz, CDCl ) δ 8.00 (d, J = 8.00 Hz, 2H), 7.60−7.57 (m, 1H),
7.42 (m, 3H), 7.39−7.35 (m, 6H), 7.24−7.20 (m, 1H), 6.98−6.94 (m,
1H), 6.49 (d, J = 8.00 Hz, 1H), 2.64−2.60 (m, 2H), 1.48−1.40 (m,
(
3
13
7
6
1
4
1
1
.53−7.44 (m, 7H), 7.27−7.25 (m, 1H), 7.18−7.12 (m, 2H), 6.91−
.87 (m, 1H), 6.23 (d, J = 8.00 Hz, 1H), 2.46−2.39 (m, 1H), 1.86−
.82 (m, 2H), 1.68−1.65 (m, 2H), 1.34−1.30 (m, 2H), 1.13−0.96 (m,
2H), 1.24−1.19 (m, 2H), 0.87−0.83 (m, 3H); C NMR (100 MHz,
CDCl ) δ 199.0, 194.4, 147.4, 140.9, 140.6, 139.5, 137.6, 137.3, 137.1,
3
136.6, 132.4, 129.9, 129.3, 129.0, 129.0, 128.6, 128.2, 124.8, 123.4,
1
3
+
H); C NMR (100 MHz, CDCl ) δ 207.5, 193.1, 147.4, 141.3,
40.3, 26.5, 22.3, 13.8; HRMS (ESI) calcd for C H O [M + Na]
3
28 24
2
41.0, 140.2, 139.4, 138.3, 137.2, 137.0, 132.8, 129.7, 129.2, 129.1,
415.1669, found 415.1692.
28.8, 128.3, 127.6, 124.9, 123.0, 49.4, 28.0, 25.8, 25.8; HRMS (ESI)
(Z)-2,2-Dimethyl-1-(1-(2-oxo-1,2-diphenylethylidene)-1H-inden-
+
calcd for C H O [M + Na] 441.1830, found 441.1846.
2-yl)propan-1-one (2x). Yield 85 mg, 72%; light-yellow solid; mp
30
26
2
1
(
Z)-2-(2-Benzoyl-1H-inden-1-ylidene)-1-(furan-2-yl)-2-phenyle-
167−168 °C; H NMR (400 MHz, CDCl
3
) δ 7.89 (d, J = 7.2 Hz, 2H),
1
thanone (2o). Yield 60 mg, 50%; yellow solid; mp 149−150 °C; H
7.49−7.46 (m, 2H), 7.43 (d, J = 7.8 Hz, 1H), 7.35−7.39 (m, 4H),
NMR (400 MHz, CDCl ) δ 7.86 (d, J = 8.00 Hz, 2H), 7.58−7.51 (m,
7.30−7.34 (m, 2H), 7.20 (t, J = 7.2 Hz, 1H), 6.91 (t, J = 7.2 Hz, 1H),
3
6.59 (d, J = 8.0 Hz, 1H), 1.21(s, 9H); 13C NMR (100 MHz, CDCl ) δ
3
6
1
1
H), 7.48−7.40 (m, 6H), 7.30−7.32 (m, 1H), 7.23−7.20 (m, 2H),
3
.99−6.95 (m, 1H), 6.85 (d, J = 4.00 Hz, 1H), 6.82 (d, J = 8.00 Hz,
208.5, 195.8, 146.6, 141.5, 139.7, 139.1, 137.1, 136.8, 135.8, 135.4,
1
3
H), 6.35−6.34 (m, 1H); C NMR (100 MHz, CDCl ) δ 192.9,
132.8, 130.2, 129.5, 129.1, 128.8, 128.2, 127.2, 124.6, 122.8, 44.1, 27.6;
3
+
82.8, 153.3, 146.8, 146.7, 145.0, 142.5, 141.0, 139.6, 139.6, 138.1,
HRMS (ESI) calcd for C H O [M + H]
393.1855, found
28
25
2
1
37.1, 136.7, 132.7, 129.7, 129.4, 129.1, 128.2, 128.0, 124.8, 123.3,
393.1861.
+
119.9, 112.2; HRMS (ESI) calcd for C H O [M + Na] 425.1154,
(Z)-2-(2-(4-Chlorobenzoyl)-1H-inden-1-ylidene)-1,2-diphenyle-
28
18
3
1
found 425.1172.
thanone (2y). Yield 97 mg, 73%; yellow solid; mp 169−170 °C; H
(
Z)-2-(2-Benzoyl-5-methyl-1H-inden-1-ylidene)-1,2-diphenyletha-
NMR (400 MHz, CDCl ) δ 7.83 (d, J = 8.00 Hz, 2H), 7.70 (d, J =
3
1
none (2p). Yield 89 mg, 70%; yellow solid; mp 135−136 °C; H NMR
8.00 Hz, 2H), 7.52−7.50 (m, 2H), 7.43−7.41 (m, 3H), 7.36−7.33 (m,
3H), 7.30−7.24 (s, 3H), 7.17 (s, 1H), 7.03−6.98 (m, 2H), 6.69 (d, J =
(
400 MHz, CDCl ) δ 7.85 (d, J = 8.00 Hz, 2H), 7.74 (d, J = 8.00 Hz,
3
2
7
H), 7.52−7.48 (m, 3H), 7.41−7.32 (m, 6H), 7.28−7.25 (m, 2H),
.14 (s, 2H), 6.80 (d, J = 8.00 Hz, 1H), 6.54 (d, J = 8.00 Hz, 1H), 2.31
8.00 Hz, 1H); 13C NMR (100 MHz, CDCl ) δ 195.5, 191.7, 146.8,
3
141.9, 140.8, 139.2, 139.0, 139.0, 137.3, 137.0, 136.8, 136.4, 132.6,
130.9, 130.1, 129.5, 129.1, 129.1, 129.0, 128.4, 128.1, 124.8, 123.4;
HRMS (ESI) calcd for C H ClO [M + Na] 469.0966, found
1
3
(
s, 3H); C NMR (100 MHz, CDCl ) δ 195.6, 193.0, 145.6, 142.4,
3
+
1
1
2
4
41.2, 139.7, 139.1, 139.0, 138.1, 137.4, 137.0, 134.5, 132.5, 132.4,
30.1, 129.8, 129.5, 129.5, 129.0, 128.8, 128.0, 128.0, 124.5, 124.0,
30
19
2
469.0952.
+
1.3; HRMS (ESI) calcd for C H O [M + Na] 449.1517, found
General Procedure for the Preparation of Compound 2z
Using a CO Balloon. An oven-dried 10 mL Schlenk tube was charged
with quinoline-based 1,6-diynol benzoate 1z (138.9 mg, 0.3 mmol)
31
22
2
49.1539.
Z)-1-(2-Benzoyl-5-fluoro-1H-inden-1-ylidene)-1-phenylpropan-
(
1
2
-one (2q). Yield 79 mg, 72%; yellow solid; mp 67−68 °C; H NMR
and PtCl (8.0 mg, 0.03 mmol) in anhydrous o-xylene (3.0 mL) under
2
1
0679
dx.doi.org/10.1021/jo5020245 | J. Org. Chem. 2014, 79, 10674−10681