Nucleobase Recognition by Artificial Receptors
J . Org. Chem., Vol. 64, No. 8, 1999 2709
6 H); 13C NMR (CDCl
) δ 168.38, 150.06, 130.52, 128.13,
δ 168.50, 81.72, 72.36, 71.19, 70.99, 69.49, 66.32, 65.70, 24.80;
3
+
MS m/e (rel intensity) 503 (M , 15%).
127.97, 127.02, 126.74, 126.66, 126.39, 120.57, 120.51, 120.37,
119.72, 96.31, 93.99, 85.30, 83.28, 72.16, 70.12, 69.89, 69.71,
65.69, 24.75; FABMS (in 3-nitrobenzyl alcohol) m/e (rel inten-
2
,6-Dia ceta m id o-4-[(1′-eth yn ylfer r ocen yl)m eth oxy]p y-
r id in e (13). To a DMSO (10 mL) solution of 12 (100 mg, 0.20
mmol) was added saturated aqueous KF solution (0.5 mL). The
reaction mixture was stirred for 1 h, poured into water, and
+
sity) 632 (MH , 74%).
NH solution of iodoferrocene10b (31
2
F er r ocep tor 3a . An Et
mg, 0.10 mmol), 7 (28 mg, 0.12 mmol), (PPh
extracted with CHCl
3 3
. The CHCl extract was evaporated and
3
)
2
PdCl
.6 µmol), and CuI (1.3 mg, 7.2 µmol) was stirred at 70 °C for
2 h. After removal of the solvent, the residue was poured into
Cl . The CH Cl extract was
evaporated and subjected to preparative thin-layer chroma-
tography (silica gel; eluent, CH Cl /MeOH 15:1) to give 3a :
yield 10% (4 mg); mp 103-106 °C (dec); IR (KBr) 2211, 1677,
2
(2.5 mg,
chromatographed (silica gel; eluent, AcOEt) to give 13: yield
3
1
9
1
3% (80 mg); mp 85-87 °C; IR (KBr) 3249, 2100, 1683, 1583,
1 1
-
438, 1240, 1155, 1041 cm ; H NMR (CDCl ) δ 7.59 (br s, 2
3
water and extracted with CH
2
2
2
2
H), 7.51 (br s, 2 H), 4.94 (s, 2 H), 4.78 (t, J ) 1.8 Hz, 2 H),
4
2
8
6
.42 (t, J ) 1.8 Hz, 2 H), 4.27-4.24 (m, 4 H), 3.06 (s, 1 H),
2
2
13
.17 (s, 6 H); C NMR (CDCl ) δ 168.66, 150.53, 96.42, 81.74,
3
0.61, 75.39, 72.30, 70.99, 70.56, 69.43, 69.33, 68.65, 66.76,
5.97, 24.75; MS m/e (rel intensity) 431 (M , 22%).
-1
1
1
7
2
1
7
612, 1550, 1413 cm ; H NMR (CDCl
3
) δ 7.98 (br s, 2 H),
+
.58 (br s, 2 H), 4.55 (t, J ) 1.7 Hz, 2 H), 4.29 (t, J ) 1.7 Hz,
3
-Iod op er ylen e (17). To a 27% aqueous H
2
SO
137 mL) of 3-aminoperylene (100 mg, 0.37 mmol) was added
an aqueous solution (30 mL) of NaNO (7.0 g, 100 mmol) at 0
C. Immediately to the reaction mixture was added a cold (ca.
4
solution
13
H), 4.25 (s, 5 H), 2.21 (s, 6 H); C NMR (CDCl ) δ 168.45,
3
1
6
(
49.44, 136.59, 132.07, 128.64, 111.25, 92.94, 85.28, 76.42,
2
4.36, 72.80, 71.17, 70.14, 65.95, 41.01, 24.85; MS m/e (rel
intensity) 401 (M , 100%).
°
+
0
°C) aqueous solution (30 mL) of KI (15 g, 90 mmol), and the
2
,6-Dia cet a m id o-4-[(1′-iod ofer r ocen yl)et h yn yl]p yr i-
reaction mixture was stirred at 0 °C for 1 h. The reaction
mixture was allowed to warm to room temperature and was
stirred at the same temperature for an additional 12 h. The
10b
d in e (19). To an i-Pr
1.05 g, 2.40 mmol), Pd
Cu(OAc) ‚H O (4.8 mg, 0.14 mmol), and PPh
mmol) was added a THF/i-Pr NH (1:1, 2 mL) mixed solution
2
NH solution of 1,1′-diiodoferrocene (18)
(dba) ‚CHCl (12.4 mg, 0.072 mmol),
(6.3 mg, 0.28
(
2
3
3
2
2
3
reaction mixture was poured into aqueous NaHSO
and extracted with CHCl . The CHCl extract was evaporated
and chromatographed (silica gel; eluent, hexane/CH Cl 5:1)
3
solution
2
3
3
of 7 (87 mg, 0.40 mmol) dropwise at 70 °C over a 2 h period.
The reaction mixture was stirred at this temperature for 12
h. After removal of the solvent, the residue was poured into
2
2
to afford crude 17: yield 11% (17 mg, 90% purity). This
compound was identified on the basis of mass spectrum and
was used for the next reaction without further purification.
F er r ocep tor 2e. A morpholine (5 mL) solution of 13 (90
water and extracted with CHCl
evaporated and chromatographed (silica gel; eluent, CH
MeOH 20:1) to afford crude 19. The crude product was washed
with CH Cl /Et O/hexane mixed solvent to give 19: yield 50%
107 mg); mp 84-86 °C; IR (KBr) 2212, 1677, 1612, 1367, 1274,
3
. The CHCl
3
extract was
2
Cl
2
/
mg, 0.21 mmol), 17 (210 mg, 0.55 mmol), (Ph
.022 mmol), and CuI (1.6 mg, 0.022 mmol) was stirred at 70
C for 12 h. After removal of the solvent, the residue was
poured into water and extracted with CHCl . The CHCl
3 2 2
P) PdCl (6 mg,
2
2
2
0
°
(
1
-1
1
3
232 cm ; H NMR (CDCl ) δ 8.02 (br s, 2 H), 7.53 (br s, 2
3
3
H), 4.53 (t, J ) 1.8 Hz, 2 H), 4.47 (t, J ) 1.8 Hz, 2 H), 4.30 (t,
extract was evaporated and chromatographed (silica gel;
eluent, AcOEt) to give crude 2e (61.4 mg). The crude product
13
J ) 1.8 Hz, 2 H), 4.25 (t, J ) 1.8 Hz, 2 H), 2.21 (s, 6 H);
NMR (CDCl ) δ 168.64, 149.50, 136.48, 111.25, 92.84, 85.30,
6.40, 74.34, 72.78, 71.17, 24.83; MS m/e (rel intensity) 527
C
3
was recrystallized from CH
2
Cl
2 2
/i-Pr O to afford 2e: yield 10%
7
(
1
15 mg); mp 160-165 °C (dec); IR (KBr) 2200, 1706, 1676,
+
(
M , 100%).
-Eth yn ylp er ylen e (23). To a morpholine (10 mL) solution
of 17 (230 mg, 0.63 mmol), (Ph P) PdCl (25 mg, 0.035 mmol),
619, 1583, 1441 cm-1; H NMR (CDCl
1
) δ 8.19-8.07 (m, 5
3
3
H), 7.68 (d, J ) 7.9 Hz, 2 H), 7.58 (d, J ) 7.9 Hz, 1 H), 7.52-
3
2
2
7
4
1
(
1
9
.48 (m, 3 H), 7.41 (br s, 2 H), 7.22 (br s, 2 H), 4.94 (s, 2 H),
and CuI (6.7 mg, 0.35 mmol) was added 3-methyl-1-butyne-
3-ol (150 mg, 1.8 mmol) at room temperature. The reaction
mixture was stirred at 100 °C for 4 h. To the mixture was
added additional 3-methyl-1-butyne-3-ol (250 mg, 3.0 mmol)
at the same temperature, and the mixture was stirred at 110
°C for 6 h. After removal of the solvent, the residue was
.64 (t, J ) 1.8 Hz, 2 H), 4.51 (t, J ) 1.8 Hz, 2 H), 4.34 (t, J )
.8 Hz, 2 H), 4.28 (t, J ) 1.8 Hz, 2 H), 2.04 (s, 6 H); 13C NMR
3
CDCl ) δ 168.38, 150.06, 130.52, 128.13, 127.97, 127.02,
26.74, 126.66, 126.39, 120.57, 120.51, 120.37, 119.72, 96.31,
3.99, 85.30, 83.28, 72.16, 70.12, 69.89, 69.71, 65.69, 24.75;
+
FABMS (in 3-nitrobenzyl alcohol) m/e (rel intensity) 681 (M ,
dissolved in water and extracted with CHCl
extract was evaporated and chromatographed (silica gel;
eluent, CHCl ) to give 3-(3-hydroxy-3-methyl-1-butynyl)-
perylene: yield 18% (38 mg); mp 162-165 °C (dec); IR (KBr)
3 3
. The CHCl
7
%).
Other oxymethylene-linked ferroceptors 2b-d were pre-
pared from 13 and 14-16, respectively, in a manner similar
to that described for 2e.
3
1
no diagnostic peaks; H NMR (CDCl
7.72-7.40 (m, 6 H), 7.33-7.28 (m, 1 H), 1.75 (s, 6 H); C NMR
CDCl ) δ 128.44, 128.28, 128.13, 126.72, 126.64, 120.94, 31.73;
FABMS (in 3-nitrobenzyl alcohol) m/e (rel intensity) 334 (M ,
0%). To NaH (9 mg, 0.22 mmol; commercial 60% dispersion
3
) δ 8.25-8.10 (m, 4 H),
2
b: yield 20%; mp 107-109 °C (dec); IR (KBr) 2200, 1682,
13
-
1 1
1
(
7
617, 1583, 1439, 1239, 1156 cm ; H NMR (CDCl
d, J ) 8.6 Hz, 2 H), 8.38 (s, 1 H), 7.99 (d, J ) 8.6 Hz, 2 H),
.63-7.45 (m, 4 H), 7.40 (br s, 2 H), 7.17 (br s, 2 H), 4.98 (s, 2
H), 4.74 (t, J ) 1.8 Hz, 2 H), 4.55 (t, J ) 1.8 Hz, 2 H), 4.41 (t,
3
) δ 8.51
(
3
+
6
1
3
was washed thoroughly with hexane prior to use) was added
a toluene solution (4 mL) of 3-(3-hydroxy-3-methyl-1-butynyl)-
perylene (70 mg, 0.21 mmol). The reaction mixture was heated
to 110 °C immediately and stirred for 10 min at that temper-
ature. The reaction mixture was poured into water and
extracted with AcOEt. The AcOEt extract was evaporated and
J ) 1.8 Hz, 2 H), 4.35 (t, J ) 1.8 Hz, 2 H), 2.08 (s, 6 H);
NMR (CDCl ) δ 168.30, 150.11, 132.30, 131.23, 128.72, 128.48,
28.13, 126.90, 126.76, 126.66, 126.37, 125.59, 118.09, 99.35,
C
3
1
9
2
6.27, 83.83, 83.11, 72.20, 70.52, 70.22, 69.83, 66.70, 65.96,
4.73; FABMS (in 3-nitrobenzyl alcohol) m/e (rel intensity) 607
+
(M , 100%).
chromatographed (silica gel; eluent, CHCl
3
) to give 23: yield
2
c: yield 15%; mp 115-118 °C (dec); IR (KBr) 2208, 1696,
-
1 1
30% (17 mg); mp 178-180 °C (dec); IR (KBr) no diagnostic
1
8
678, 1620, 1585, 1440, 1238, 1155 cm ; H NMR (CDCl
3
) δ
1
peaks; H NMR (CDCl
H), 3.55 (s, 1 H); 13C NMR (CDCl
127.91, 126.60, 120.27.
3
) δ 8.25-8.06 (m, 5 H), 7.74-7.45 (m,
.48 (d, J ) 8.6 Hz, 1 H), 8.19 (d, J ) 8.6 Hz, 2 H), 8.14-8.01
6
3
) δ 134.84, 131.33, 128.88,
(m, 6 H), 7.36 (br s, 2 H), 7.00 (br s, 2 H), 4.98 (s, 2 H), 4.70 (s,
2
H), 4.55 (s, 2 H), 4.38 (s, 2 H), 4.32 (s, 2 H), 1.98 (s, 6 H); 13
C
Ethynylarenes 21 and 22 were synthesized from 15 and 16,
respectively, via corresponding (3-hydroxy-3-methyl-1-butyn-
yl)arenes in a manner similar to that described for 23.
NMR (CDCl ) δ 168.34, 168.10, 149.92, 131.34, 129.41, 127.99,
3
1
7
27.73, 127.30, 126.13, 125.75, 125.35, 125.27, 124.39, 96.25,
2.20, 70.14, 69.87, 69.69, 24.67; FABMS (in 3-nitrobenzyl
+
alcohol) m/e (rel intensity) 631 (M , 75%).
1-(3-Hyd r oxy-3-m eth yl-1-bu tyn yl)p yr en e: yield 60%;
1
2
d : yield 10%; mp 177-179 °C (dec); IR (KBr) 2200, 1696,
mp 104-105 °C (dec); IR (KBr) no diagnostic peaks; H NMR
-
1 1
1
7
4
580, 1544, 1444, 1248, 1155 cm ; H NMR (CDCl
3
) δ 8.20-
(CDCl ) δ 8.38 (d, J ) 9.2 Hz, 1 H), 8.03-7.78 (m, 8 H), 2.73
3
13
.95 (m, 9 H), 7.48 (br s, 2 H), 7,21 (br s, 2 H), 5.00 (s, 2 H),
.63 (s, 2 H), 4.53 (s, 2 H), 4.34 (s, 2 H), 4.30 (s, 2 H), 1.98 (s,
(s, 1 H), 1.78 (s, 6 H); C NMR (CDCl
3
) δ 131.75, 131.02,
130.82, 129.47, 128.15, 127.91, 127.00, 126.01, 125.42, 125.38,