ꢀ
Sanchez-Larios and Gravel
JOCNote
temperature. The reaction was then quenched with a saturated
aqueous solution of ammonium chloride (2 mL) and extracted
with CH2Cl2 (3 ꢀ 5 mL). The combined organic extracts were
dried over anhydrous sodium sulfate, and the solvent was re-
moved in vacuo. The crude product was purified by flash column
chromatography on silica gel (40% hexanes/CH2Cl2), yielding
34.1mgof 3aa0 and8.4mgof 4aa0 (64% combinedyield). 3aa0 was
obtained as white crystals (recrystallized from CH2Cl2/2-
propanol): mp 115-116 °C; Rf 0.35 (100% CH2Cl2); FTIR
dro-1H-indene-1,2-diyl)bis(phenylmethanone) (3aa0:4aa0, dr =
80:20) (100 mg, 0.225 mmol) in THF/MeOH (2:3, 0.5 mL, 0.5 M)
containing powdered 4 A molecular sieves (25 mg) was heated to
70 °C. Aniline (13) (61.5 μL, 0.675 mmol) was then added,
followed by p-toluenesulfonic acid monohydrate (42.8 mg,
0.225 mmol). The flask was fitted with a reflux condenser and
the mixture was stirred at 70 °C for 48 h. The resulting mixture
was then diluted with ethyl acetate (3 mL) and saturated aqueous
ammonium chloride (5 mL). The organic layer was washed with
brine, and then dried over anhydrous sodium sulfate. The solvent
was removed in vacuo and the crude mixture was purified by flash
column chromatography on silica gel (10% ethyl acetate/hexanes)
yielding a white-yellow solid (50.4 mg, 45%), mp 216-217 °C:
Rf 0.45 (30/70 ethyl acetate/hexanes); FTIR (KBr film) 3055,
1682, 1597, 1495, 1443, 1355 cm-1; 1H NMR (500 MHz, CDCl3)
δ 7.81 (d, J=7.3 Hz, 2H), 7.51-7.48 (m, 2H), 7.41 (d, J=7.5 Hz,
1H), 7.37 (dd, J = 7.8, 7.5 Hz, 2H), 7.30-7.25 (m, 5H), 7.24-
7.19 (m, 3H), 7.17-7.15 (m, 5H), 7.11-7.03 (m, 4H), 5.08 (dd,
J = 9.3, 3.5 Hz, 1H), 3.33 (dd, J = 17.3, 3.7 Hz, 1H), 3.24 (dd,
J = 17.3, 9.4 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 199.8,
151.3, 139.1, 137.4, 133.1, 132.8, 132.5, 132.1, 130.2, 129.3,
129.2, 129.0, 128.8, 128.6, 128.4, 128.3, 128.2, 127.6, 127.2,
127.1, 127.0, 126.6, 126.1, 125.7, 125.5, 119.7, 42.4, 38.3.
HRMS (EIþ) m/z calcd for C37H27NO [Mþ] 501.2092, found
501.2084.
1
(KBr film) 3064, 1680, 1596, 1579, 1448, 1217 cm-1; H NMR
(500 MHz, CDCl3) δ 8.18 (d, J=7.7 Hz, 2H), 8.07 (d, J=7.7 Hz,
2H), 7.74 (d, J = 7.7 Hz, 2H), 7.66 (dd, J = 7.4, 7.4 Hz, 1H),
7.61-7.55 (m, 3H), 7.51-7.47 (m, 3H), 7.36 (dd, J=7.3, 7.3 Hz,
2H), 7.29 (d, J=7.5 Hz, 1H), 7.16 (t, J=7.4 Hz, 1H), 7.08 (dd,
J=7.4 Hz, 1H), 6.89 (d, J=7.5 Hz, 1H), 5.90 (d, J=9.6 Hz, 1H),
5.30 (dd, J=8.8, 8.8 Hz, 1H), 4.56 (ddd, J=7.8, 7.8, 6.2 Hz, 1H),
3.14 (dd, J=17.2, 8.6Hz, 1H), 3.10(dd, J=17.2, 5.4Hz, 1H);13
C
NMR (125 MHz, CDCl3) δ 200.3, 199.2, 198.1, 145.5, 140.3,
137.9, 137.1, 136.8, 133.9, 133.9, 133.3, 129.5, 129.2, 129.1, 128.8,
128.7, 128.2, 128.1, 127.8, 125.6, 124.4, 54.1, 52.4, 42.5, 41.1;
HRMS (EIþ) m/z calcd for C31H24O3 [Mþ] 444.1725, found
444.1726. 4aa0 was obtained as a pale yellow foam: mp 48-49 °C;
Rf 0.28 (100% CH2Cl2); FTIR (KBr film) 3342, 3065, 2928, 1681,
1596, 1580, 1480 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.01 (d,
J = 7.3 Hz, 2H), 7.95 (d, J = 7.3 Hz, 2H), 7.92 (d, J = 7.3 Hz,
2H), 7.62 (dd, J = 7.4, 7.4 Hz, 1H), 7.55 (t, J = 7.4 Hz, 1H), 7.50
(t, J = 7.6 Hz, 3H), 7.43 (dd, J = 7.8, 7.8 Hz, 2H), 7.38 (dd, J =
7.6, 7.6 Hz, 2H), 7.25 (d, J = 7.5Hz, 1H), 7.21(t, J = 7.3 Hz, 1H),
7.08 (t, J = 7.4 Hz, 1H), 6.89 (d, J = 7.7 Hz, 1H), 5.46 (d, J =
5.5 Hz, 1H), 4.74 (dd, J = 5.5, 5.5 Hz, 1H), 4.46 (ddd, J = 6.7,
6.4, 6.4 Hz, 1H), 3.61 (dd, J = 17.6, 6.0 Hz, 1H), 3.60 (dd, J =
17.7, 7.8 Hz, 1H); 13C NMR (125 MHz, CDCl3) δ 201.1, 199.4,
198.8, 145.7, 139.8, 137.2, 137.1, 136.9, 133.9, 133.4, 133.3, 129.5,
129.1, 128.9, 128.9, 128.8, 128.3, 127.6, 124.8, 124.8, 56.3, 54.3,
45.2, 43.8; HRMS (EIþ) m/z calcd for C31H24O3 [Mþ] 444.1725,
found 444.1708.
Acknowledgment. We thank the Natural Sciences and
Engineering Research Council of Canada (NSERC), the
Canada Foundation for Innovation, and the University of
Saskatchewan for financial support. Dr. Gabriele Schatte is
acknowledged for X-ray crystallographic analysis.
Supporting Information Available: Experimental proce-
dures, characterization data, NMR spectra for all new com-
pounds, ORTEP representation, and a CIF file for 3aa0. This
material is available free of charge via the Internet at http://
pubs.acs.org.
Synthesis of 1-Phenyl-2-(1,2,3-triphenyl-2,8-dihydroindeno-
[1,2-c]pyrrol-8-yl)ethanone (14). In a Schlenk flask fitted with a
septum, a stirred solution of 3-(2-oxo-2-phenylethyl)-2,3-dihy-
J. Org. Chem. Vol. 74, No. 19, 2009 7539