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Y. Ishii et al. / Tetrahedron 71 (2015) 8892e8898
4.5. 2-Chloro-1,2,3,4-tetrahydro-3-(phenylsulfonyl)-1,4-etha-
nonaphthalene (6)
123.25, 108.92, 37.60, 28.59; IR (cmꢁ1):
n
¼3384, 2958; ESI (m/z) 196
(MþHþ); Elemental Anal. Calcd for C16H13NO2. C, 76.48; H, 5.21; N,
5.57. Found: C, 76.11; H, 4.99; N, 5.88.
A solution of 5 (11.02 g, 36.63 mmol) in CHCl3 (300 mL) was
cooled to 0 ꢀC and m-CPBA (21.4 g, 80.60 mmol) was added. The
reaction was warmed to room temperature and stirred overnight.
The reaction was quenched with saturated aqueous NaHSO3. The
organic layer was washed with saturated aqueous NaHCO3, water,
and brine, and dried over anhydrous Na2SO4. After evaporation, the
product was precipitated from Et2O to provide 6.08 g (50%) of 6 as
4.9. 4,9-Dihydro-4,9-ethano-2H-benz[f]isoindole-2,5-
dicarboxyaldehyde (16)
4,9-Dihydro-4,9-ethano-2H-benz[f]isoindole
9
(0.105
g,
0.54 mmol) was dissolved in CF3COOH (1.1 ml) under N2 and pro-
tection from light. The mixture was stirred at 0 ꢀC for 5 min before
freshly distilled trimethyl orthoformate (1.1 ml) was slowly added.
The stirring was kept at 0 ꢀC for 1 h, then mixture was poured into
water (4 ml). 20% NaOH was then added until the pH was natural.
The solution was extracted with CHCl3 (20 ml), and extract was
washed with water (50 ml) and dried over anhydrous Na2SO4, After
evaporation, the residue was purified by column chromatography
on silica gel (CHCl3) to provide 0.12 g (85%) of 16 as pale yellow
colorless crystals. 1H NMR (CDCl3, 500 MHz, ppm):
d¼7.81 (m, 2H),
7.64 (m, 1H), 7.53 (m, 2H), 7.27 (m, 3H), 7.18 (m, 1H), 4.19 (ddd, 1H),
3.69 (dt, 1H), 3.51 (dd, 1H), 3.27 (q, 1H), 2.30 (m, 1H), 1.93 (ddt, 1H),
1.54 (m, 1H), 1.39 (m, 1H); 13C NMR (CDCl3, 125 MHz, ppm):
d
¼138.85, 138.31, 138.01, 134.08, 129.39, 128.92, 127.86, 127.85,
127.59, 125.54, 124.46, 72.68, 57.05, 42.97, 34.76, 26.91, 18.24; IR
(cmꢁ1):
n
¼2963,1558,1507; ESI (m/z) 333 (MþHþ); Elemental Anal.
Calcd for C18H17O2SCl. C, 64.95; H, 5.15. Found: C, 64.62; H, 5.14.
powder. 1H NMR (CDCl3, 270 MHz, ppm):
1H), 7.30 (m, 2H), 7.15 (m, 2H), 4.73 (s, 2H), 1.84 (m, 4H); 13C NMR
(CDCl3, 125 MHz, ppm):
¼179.95, 143.09, 139.84, 127.65, 126.56,
d¼9.92 (s, 2H), 9.65 (brs,
4.6. 1,4-Dihydro-2-(phenylsulfonyl)-1,4-ethanonaphthalene
(7)
d
124.05, 36.80, 27.60; IR (cmꢁ1):
n
¼3261, 2925, 1679; MALDI-TOF
(m/z) 252 (MþHþ); Elemental Anal. Calcd for C14H13N. C, 86.12; H,
A solution of 6 (4.52 g, 13.58 mmol) in dry pyridine (30 mL) was
cooled to 0 ꢀC and DBU (2.24 mL, 14.16 mmol) was added under Ar
over 2 h. The organic layer was washed with 1 M HCl, water, and
brine, and dried over anhydrous Na2SO4. After evaporation, the
product was dried to provide 4.00 g (99%) of 7 as yellow oil. 1H NMR
6.71; N, 7.17. Found: C, 86.10; H, 6.56; N, 7.00.
4.10. [1,2]Benzenobicyclo[2.2.2]octadieneporphyrin (10a)
A solution of 8 (2.01 g, 7.50 mmol) in dry THF (100 mL) was
cooled to 0 ꢀC under Ar and LiAlH4 (0.85 g, 20.60 mmol) was added.
The reaction mixture was stirred for 2 h at 0 ꢀC. The reaction was
quenched water, and then filtered through Celite. CHCl3 (2.5 L) was
added to the combined extracts and 1 M HCl was added dropwise
as an acid catalyst. The solution was stirred overnight at room
temperature, and then p-chloranil (0.85 g, 3.46 mmol) was added.
The mixture was stirred for 1 h at room temperature, and then
washed with saturated aqueous NaHCO3, water, and brine, and
dried over anhydrous Na2SO4. After evaporation, the residue was
purified by column chromatography on alumina and silica gel
(CHCl3) and then precipitated from methanol to provide 0.91 g
(59%) of 10a as purple powder. 1H NMR (CDCl3, 500 MHz, ppm):
(CDCl3, 500 MHz, ppm):
7.16 (m, 1H), 7.08 (dt, 1H), 7.02 (dt, 1H), 6.95 (m, 1H), 4.21 (m, 2H),
1.67e1.42 (m, 4H); 13C NMR (CDCl3, 125 MHz, ppm):
d¼7.80 (m, 2H), 7.57 (m, 1H), 7.48 (m, 3H),
d
¼168.25,
167.91, 147.27, 144.94, 143.58, 139.25, 133.74, 130.41, 129.84, 129.49,
127.92, 123.83, 123.44, 52.81, 41.39, 40.49, 25.80, 25.17; IR (cmꢁ1):
n
¼2951, 1725; ESI (m/z) 297 (MþHþ); ESI-HRMS (m/z) (MþHþ);
Elemental Anal. Calcd for C18H16O2S, 297.0944; Found, 297.0939.
4.7. Ethyl-4,9-dihydro-4,9-ethano-2H-benz[f]isoindole-1-
carboxylate (8)
A solution of 7 (4.00 g, 13.50 mmol) in dry THF (50 mL) was
cooled to 0 ꢀC, and CNCH2CO2Et (1.68 mL, 13.50 mmol) and 1 M t-
BuOK in THF (14.8 mL, 14.80 mmol) were added under Ar. The re-
action was warmed to room temperature and stirred for 5 h. The
reaction was quenched with 1 M HCl. The organic layer was washed
with 1 M HCl, water, and brine, and dried over anhydrous Na2SO4.
After evaporation, the residue was purified by column chroma-
tography on silica gel (CHCl3) to provide 2.68 g (74%) of 8 as col-
d
¼10.52 (m, 4H), 7.79 (m, 8H), 7.23 (m,8H), 6.17 (s, 8H), 2.41 (m, 8H),
2.25 (m, 8H), ꢁ4.66 (br s, 2H); UVevis (CHCl3), lmax (log
3
): 392
(5.22), 496 (4.24), 527 (3.88), 564 (3.83), 616 (3.25); MALDI-TOF (m/
z) 823 (Mþ); Elemental Anal. Calcd for C60H46N4$H2O. C, 85.68; H,
5.75; N, 6.66. Found: C, 85.59; H, 5.55; N, 6.53.
4.11. [1,2]Benzenobicyclo[2.2.2]octadieneporphyrin zinc
complex (10b)
orless crystals. 1H NMR (CDCl3, 500 MHz, ppm):
d
¼8.38 (brs, 1H),
7.27 (m, 1H), 7.21 (m, 1H), 7.09 (m, 2H), 6.66 (dd, 1H), 4.79 (brt, 1H),
4.33 (dq, 2H), 4.28 (brt,1H), 1.76e1.69 (m, 4H), 1.40 (t, 3H); 13C NMR
A solution of 10a (40.0 mg, 48.68
mmol) and Zn(OAc)2$2H2O
(CDCl3, 125 MHz, ppm):
d
¼145.15, 144.42, 130.82, 125.64, 125.59,
(20.0 mg, 91.11 mol) in CHCl3 (40 mL) and MeOH (3 mL) was
m
123.81, 123.20, 114.93, 113.74, 60.11, 37.90, 37.51, 28.07, 27.43, 14.73;
stirred for 3 h. The organic layer was washed with water and brine,
and dried over anhydrous Na2SO4. After evaporation, the residue
was purified by column chromatography on silica gel (CHCl3) and
then precipitated from methanol to give a quantitative yield of 10b
IR (cmꢁ1):
n
¼3309, 2955, 1683, 1317, 1220, 1144; ESI (m/z) 268
(MþHþ); Elemental Anal. Calcd for C17H17NO2. C, 76.38; H, 6.41; N,
5.24. Found: C, 76.27; H, 6.43, N, 5.22.
as a red powder. 1H NMR (CDCl3, 500 MHz, ppm):
d
¼10.59 (m, 4H),
7.81e7.79 (m, 8H), 7.25e7.22 (m, 8H), 6.21 (s, 8H), 2.45e2.29 (m,
16H); UVevis (CHCl3), lmax (log ): 404 (5.45), 529 (4.28), 563
(4.19); MALDI-TOF (m/z) 885 (Mþ); Elemental Anal. Calcd for
60H44N4Zn$2H2O. C, 78.12; H, 5.24; N, 6.07. Found: C, 78.26; H,
4.8. 4,9-Dihydro-4,9-ethano-2H-benz[f]isoindole (9)
3
A mixture of 8 (2.50 g, 9.35 mmol) and NaOH (2.50 g,
60.63 mmol) in ethylene glycol (50 mL) was heated at 160 ꢀC for 3 h
in the dark. The reaction was quenched with 1 M HCl. The organic
layer was washed with water, NaHCO3, and brine, and dried over
anhydrous Na2SO4. After evaporation, the residue was purified by
column chromatography on silica gel (CHCl3) to provide 1.78 g
C
5.52; N, 5.96.
4.12. [1,2]Benzenobicyclo[2.2.2]octadieneporphyrin copper
complex (10c)
(98%) of 9 as white powder. 1H NMR (CDCl3, 500 MHz, ppm):
(brs, 1H), 7.20 (m, 2H), 7.05 (m, 2H), 6.54 (d, 2H), 4.27 (s, 2H), 1.74
(m, 4H); 13C NMR (CDCl3, 125 MHz, ppm):
¼145.76, 128.62, 125.37,
d
¼7.55
A solution of 10a (40.0 mg, 48.68
mmol) and Cu(OAc)2$H2O
d
(24.3 mg, 133.79 mol) in CHCl3 (40 mL) and MeOH (3 mL) was
m