K. Tomizaki et al. / Tetrahedron 59 (2003) 1191–1207
1205
temperature and then passed through a silica column
[CHCl3/hexanes (4:1)]. The resulting residue was further
purified by preparative SEC (THF) followed by column
chromatography [silica, CHCl3/hexanes (9:1)] to yield a
After 30 min, DDQ (123 mg, 542 mmol) was added and the
mixture was stirred at room temperature for 1 h. Triethyl-
amine was added to the reaction mixture and the resulting
mixture was filtered through a silica column [CH2Cl2/
hexanes (2:1)]. The resulting residue was dissolved in
CH2Cl2 (40 mL) and the mixture was treated with a solu-
tion of Zn(OAc)2·2H2O (201 mg, 917 mmol) in methanol
(10 mL) at room temperature. After 15 h, the mixture was
washed with water, dried (Na2SO4), then chromatographed
[silica, CH2Cl2/hexanes (2:1)]. The desired fraction was
collected and concentrated. The resulting solid was treated
with methanol and the suspension was sonicated for
1
magenta solid (457 mg, 69%): H NMR d 1.31 (s, 18H),
1.34 (s, 18H), 1.35 (s, 18H), 6.85 (d, J¼8.8 Hz, 2H), 7.00 (d,
J¼8.8 Hz, 4H), 7.06 (d, J¼8.8 Hz, 4H), 7.10 (d, J¼8.8 Hz,
4H), 7.27 (d, J¼8.8 Hz, 4H), 7.36 (d, J¼8.8 Hz, 4H), 7.40–
7.43 (m, 8H), 7.57–7.62 (m, 4H), 7.64 (d, J¼8.8 Hz, 4H),
7.91–7.96 (m, 3H), 8.18 (s, 2H), 8.21 (s, 2H), 8.45 (d,
J¼8.4 Hz, 2H), 9.20 (d, J¼8.8 Hz, 2H), 9.41 (d, J¼8.0 Hz,
2H), 9.98 (s, 1H); 13C NMR d 29.4, 29.7, 31.43, 31.45, 31.5,
34.37, 34.41, 34.44, 87.8, 91.0, 111.5, 118.4, 118.6, 119.8,
119.9, 120.8, 121.9, 122.7, 122.8, 124.0, 124.2, 124.7,
125.6, 126.4, 126.9, 127.07, 127.14, 127.3, 127.5, 127.6,
129.0, 129.7, 129.8, 130.4, 131.2, 132.0, 132.4, 135.5,
136.5, 139.5, 147.0, 147.2, 147.5, 152.6, 153.4, 155.9,
163.1, 190.7; MALDI-MS (POPOP) obsd 1834.3 [Mþ],
calcd avg mass 1834.2 (C127H104N2O12); labs 415, 533; lem
(lex¼420 nm) 575, 625 (sh) nm.
1
10–20 s. Filtration afforded a red solid (45 mg, 10%): H
NMR d 1.28 (s, 18H), 1.30 (s, 18H), 1.34 (s, 18H), 1.84 (s,
6H), 2.64 (s, 3H), 3.31 (s, 1H), 6.89 (d, J¼9.2 Hz, 2H), 7.00
(d, J¼8.4 Hz, 4H), 7.05–7.10 (m, 8H), 7.26–7.29 (m, 6H),
7.35 (d, J¼8.8 Hz, 4H), 7.40 (d, J¼8.8 Hz, 4H), 7.41 (d,
J¼8.8 Hz, 4H), 7.58–7.65 (m, 2H), 7.68 (d, J¼8.4 Hz, 4H),
7.84–7.93 (m, 4H), 8.05 (d, J¼8.0 Hz, 2H), 8.15 (d, J¼
8.8 Hz, 2H), 8.18–8.19 (m, 1H), 8.22 (s, 2H), 8.24 (s, 2H),
8.37–8.38 (m, 2H), 8.47 (d, J¼8.4 Hz, 2H), 8.81 (d, J¼
4.8 Hz, 2H), 8.87 (d, J¼4.4 Hz, 2H), 8.91–8.92 (m, 2H),
8.99 (d, J¼4.8 Hz, 2H), 9.25 (d, J¼8.8 Hz, 2H), 9.45 (d, J¼
8.4 Hz, 2H); MALDI-MS (dithranol) obsd 2597.2 [Mþ],
calcd avg mass 2598.2 (C169H131IN6O10Zn); labs 427
(fwhm¼13 nm), 535 nm; lem (lex¼540 nm) 598, 646 nm.
4.3.17. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]di-
pyrromethane (23). Following a standard procedure29 with
slight modification,21 a solution of 22 (500 mg, 273 mmol)
in CH2Cl2 (2.7 mL) was treated with pyrrole (8.0 mL,
0.11 mol) followed by TFA (2.1 mL, 27 mmol). The mixture
was stirred at room temperature. After 15 min, triethylamine
(2 mL) and CH2Cl2 (20 mL) were added. The reaction
mixture was washed with brine, dried over Na2SO4 and
purified by column chromatography (silica, CHCl3),
4.3.19. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]-10,
20-bis(4-ethynylphenyl)-15-mesitylporphinatozinc(II)
(17). Following a standard procedure28 with improved acid
catalysis conditions,31 a sample of 25 (54.0 mg, 103 mmol)
was reduced with NaBH4 (78.0 mg, 2.05 mmol) in
THF/methanol [5 mL (10:1)]. The resulting dipyrro-
methane–dicarbinol (25-diol) was reacted with 23
(200 mg, 103 mmol) in CH2Cl2 (40 mL) in the presence of
Yb(OTf)3 (83.0 mg, 134 mmol) at room temperature. After
20 min, the reaction mixture was treated with DDQ
(70.0 mg, 308 mmol) and stirred for 1 h. Triethylamine
was then added and the mixture was filtered through a silica
column [CH2Cl2/hexanes (2:1)]. The resulting residue was
dissolved in CHCl3 (20 mL) and the mixture was treated
with a solution of Zn(OAc)2·2H2O (113 mg, 513 mmol) in
methanol (5.0 mL) at room temperature. After 2 h, the
mixture was washed with water, dried (Na2SO4) and
chromatographed [silica, CH2Cl2/hexanes (2:1)] affording
a red solid (30 mg, 31%): 1H NMR d 0.99 (s, 18H), 1.01 (s,
18H), 1.21 (s, 18H), 1.84 (s, 6H), 2.31 (s, 2H), 2.96–2.98
(m, 3H), 6.57 (d, J¼9.2 Hz, 2H), 6.67 (d, J¼8.8 Hz, 4H),
6.72–6.77 (m, 6H), 6.93–7.09 (m, 12H), 7.31 (d, J¼7.6 Hz,
4H), 7.36 (d, J¼7.6 Hz, 4H), 7.50–7.54 (m, 5H), 7.83–7.84
(m, 4H), 7.90 (d, J¼10.0 Hz, 4H), 8.05 (s, 2H), 8.15 (d,
J¼8.0 Hz, 4H), 8.49–8.67 (m, 12H), 8.93 (d, J¼8.8 Hz,
2H), 9.13 (d, J¼7.6 Hz, 2H), 9.68 (s, 2H); MALDI-MS
(dithranol) obsd 2497.5 [(MþH)þ], calcd avg mass 2496.3
(C171H132N6O10Zn); labs 427 (fwhm¼13 nm), 536 nm; lem
(lex¼540 nm) 598, 647 nm.
1
affording a magenta solid (510 mg, 96%): H NMR d 1.32
(s, 18H), 1.34 (s, 18H), 1.35 (s, 18H), 5.48 (s, 1H), 5.95–
5.98 (m, 2H), 6.19 (dd, J 1¼4.4 Hz, J 2¼2.4 Hz, 2H), 6.26
(dd, J 1¼4.4 Hz, J 2¼2.4 Hz, 1H), 6.83 (dd, J 1¼4.4 Hz,
J 2¼2.4 Hz, 1H), 6.89 (d, J¼9.2 Hz, 4H), 7.00 (d, J¼8.8 Hz,
4H), 7.06 (d, J¼9.2 Hz, 4H), 7.09 (d, J¼8.8 Hz, 4H), 7.26
(d, J¼8.8 Hz, 4H), 7.36 (d, J¼8.8 Hz, 4H), 7.39–7.44 (m,
9H), 7.62 (d, J¼8.8 Hz, 4H), 7.64–7.65 (m, 2H), 8.01 (brs,
2H), 8.21 (s, 2H), 8.23 (s, 2H), 8.48 (dd, J 1¼8.0 Hz,
J 2¼1.2 Hz, 2H), 9.25 (d, J¼8.8 Hz, 2H), 9.25 (d, J¼8.8 Hz,
2H), 9.44 (dd, J 1¼8.0 Hz, J 2¼1.2 Hz, 2H); 13C NMR d
29.7, 31.43, 31.45, 31.5, 34.38, 34.41, 34.44, 43.6, 89.2,
89.7, 107.6, 108.6, 111.6, 117.7, 118.4, 118.6, 119.8, 120.0,
120.9, 122.1, 122.8, 123.3, 123.7, 124.1, 124.3, 125.8,
126.5, 126.9, 127.09, 127.15, 127.3, 127.57, 127.63, 128.8,
129.8, 129.9, 130.5, 130.9, 131.3, 131.5, 132.0, 132.4,
133.5, 135.2, 142.8, 147.1, 147.2, 147.5, 152.7, 153.37,
153.40, 153.45, 153.54, 156.0, 163.2; MALDI-MS (dithra-
nol) obsd 1950.7 [Mþ], calcd avg mass 1950.4
(C135H112N4O2); labs 414, 531 nm; lem (lex¼540 nm)
574, 621 (sh) nm.
4.3.18. 5-[3,5-Bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)-
perylene-3,4-dicarboximido]phenyl]ethynyl]phenyl]-10-
(4-ethynylphenyl)-20-(4-iodophenyl)-15-mesitylporph-
inatozinc(II) (16). Following a standard procedure28 with
improved acid catalysis conditions,31 a sample of 24
(112 mg, 179 mmol) was reduced with NaBH4 (136 mg,
3.60 mmol) in THF/methanol [20 mL (10:1)]. The resulting
dipyrromethane–dicarbinol (24-diol) was condensed with
23 (344 mg, 179 mmol) in CH2Cl2 (7.0 mL) in the presence
of Yb(OTf)3 (145 mg, 234 mmol) at room temperature.
4.3.20. Sonogashira oligomerization of 16. Following a
standard procedure,21 a mixture of 16 (20 mg, 7.7 mmol),
Pd2(dba)3 (1.1 mg, 1.2 mmol) and AsPh3 (2.8 mg, 9.2 mmol)
in toluene/triethylamine [3 mL (5:1)] was stirred under
argon at room temperature for 40 h. The reaction