Molecular Recognition with Ditopic Cavitand Re Complexes
Monophosphonate Cavitands 11i and 11o: 4-Iodophenylphosphonic
dichloride (216 mg, 0.68 mmol) and triethylamine (189 μL,
1.36 mmol) were added under nitrogen to a solution of the resor-
cinarene 10 (385 mg, 0.34 mmol) in dry toluene (20 mL). The mix-
ture was stirred at 50 °C overnight. After evaporation of the sol-
vent, the crude product was purified by column chromatography
on silica gel with hexane/ethyl acetate (7:3, v/v) as eluent to give 11i
as a pale yellow solid (69 mg, 0.0485 mmol, 17%).
ethyl acetate (9:0.5:0.5, v/v) as eluent to give 4 as a solid in 56%
yield (16 mg, 0.00519 mmol). 1H NMR (300 MHz, CDCl3): δ =
8.82 (d, J = 6.7 Hz, XXЈ part of an AAЈXXЈ system, 4 H, PyHo),
3
8.09–8.01 (m, AAЈ part of an AAЈBBЈ system, 4 H, POArHo), 7.74–
7.70 (m, BBЈ part of an AAЈBBЈ system, 4 H, POArHm), 7.41 (d,
3J = 6.6 Hz, AAЈ part of an AAЈXXЈ system, 4 H, PyHm), 7.14 (s,
4 H, ArHdown), 7.09 (s, 4 H, ArHdown), 6.66 (s, 4 H, ArHup), 6.53
(s, 4 H, ArHup), 5.76 (d, 2J = 7.3 Hz, 2 H, CHout), 5.65 (d, 2J =
7.2 Hz, 4 H, CHout), 4.76 (t, 4 H, RCHAr2), 4.69–4.63 (m, 6 H,
CHin, 4 H, RCHAr2), 2.33–2.19 (m, 16 H, CHCH2R), 1.36–1.17
(m, 144 H, CH2), 0.86 (m, 24 H, CH3) ppm. 31P NMR (162 MHz,
1
Isomer 11i: H NMR (600 MHz, CDCl3): δ = 7.97–7.95 (m, AAЈ
3
part of an AAЈBBЈ system, 2 H, POArHm), 7.78–7.75 [dd, J(P,H)
= 13.8, 3J = 8.4 Hz, part of an AAЈBBЈ system, 2 H, POArHo],
CDCl ): δ = 6.17 (s, 1 P, POPh) ppm. FT–IR: ν = 2029, 1929, 1892
˜
3
4
7.18 (s, 2 H, ArHdown), 7.13 (s, 2 H, ArHdown), 6.68 [s, J(P,H) =
(C=O) cm–1. MS (ESI): m/z (%) calcd. for C179H236BrN2O21P2Re
[M] 3079.9, calcd. for [M – Br]+ 3000.0; found 3000.2 (100), calcd.
for [M + H]+ 3080.9; found 3080.0 (80). C179H236BrN2O21P2Re
(3079.89): calcd. C 69.81, H 7.72, N 0.91; found C 69.54, H 8.11,
N 1.22.
2
1.4 Hz, 2 H, ArHup], 6.57 (s, 2 H, ArHup), 5.80 (d, J = 7.2 Hz, 1
2
3
H, CHout), 5.70 (d, J = 7.2 Hz, 2 H, CHout), 4.80 (t, J = 7.8 Hz,
2 H, RCHAr2), 4.74–4.71 (m, 3 H, CHin, RCHAr2), 4.69–4.67 (m,
2 H, CHin, RCHAr2), 2.15–2.10 (m, 8 H, CHCH2R), 1.50–1.25 (m,
72 H, CH2), 0.89 (m, 12 H, CH3) ppm. 31P NMR (162 MHz,
CDCl3): δ = 6.15 (s, 1 P, POAr) ppm. MS (ESI): m/z (%) calcd. for
C81H114IO9P [M] 1387.9, calcd. for [M + HN(C2H5)3]+ 1490.9;
found 1491.2 (100), calcd. for [M + Na]+ 1411.7; found 1412.1 (70),
calcd. for [M + K]+ 1427.7; found 1428.1 (20).
Dithiophosphonate Cavitand 13aout: A mixture of the resorcinarene
12a (195 mg, 0.14 mmol), K2CO3 (195 mg, 1.41 mmol) and 4-(α,α-
dibromotolyl)pyridine (184 mg, 0.56 mmol) in dry DMF (10 mL)
was stirred in a sealed tube at 85 °C for 19 h. The reaction mixture
Isomer 11o: 1H NMR (600 MHz, CDCl3): δ = 7.22 (s, 2 H, was then allowed to cool, poured into water and extracted with
ArHdown), 7.19 (s, 2 H, ArHdown), 6.58–6.56 (m, POArHm, AAЈ
part of an AAЈBBЈ system, 2 H, ArHup), 6.09 [s, 4J(P,H) = 1.8 Hz,
2 H, ArHup], 5.93 [dd, 3J(P,H) = 12.0, 3J = 9.0 Hz, part of an
CH2Cl2. Removal of the solvent gave a solid, which was purified
by column chromatography on silica gel with CH2Cl2/EtOH
(99:1, v/v) as eluent to give 13aout in a 53% yield (127 mg,
0.07 mmol), m.p. 104–106 °C. 1H NMR (300 MHz, CDCl3): δ =
2
AAЈBBЈ system, 2 H, POArHo], 5.86 (d, J = 7.3 Hz, 1 H, CHout),
2
5.60 (d, J = 7.3 Hz, 2 H, CHout), 4.76 (m, 1 H, RCHAr2), 4.72 (t, 8.68 (m, AAЈ part of an AAЈXXЈ system, 4 H, PyHo), 8.21 [dd,
2
3J = 8.4 Hz, 3 H, RCHAr2), 4.48 (d, J = 7.3 Hz, 1 H, CHin), 3.76
3J(P,H) = 14.9, 3J = 8.4 Hz, 4 H, POArH], 7.80 (d, AAЈ part of an
AAЈBBЈ system, 4 H, ArHPy), 7.67 (m, BBЈ part of an AAЈBBЈ
2
(d, J = 7.3 Hz, 2 H, CHin), 2.26 (m, 2 H, CHCH2R), 2.20 (m, 6
H, CHCH2R), 1.31–1.24 (m, 72 H, CH2), 0.86 (t, 3J = 6.6 Hz, system, 6 H, ArHPy, POArH), 7.58 (m, XXЈ part of an AAЈXXЈ
12 H, CH3) ppm. 31P NMR (162 MHz, CDCl3): δ = 2.72 (s, 1 P,
POAr) ppm. HR-ESI-MS: m/z calcd. for C81H115IO9P+
1389.73179; found 1389.72181 [M + H]+.
system, 8 H, PyHm, POArH), 7.30 (s, 4 H, ArHdown), 6.79 [s,
4J(P,H) = 2.0 Hz, 4 H, ArHup], 5.69 (s, 2 H, RCHArPy), 4.88 (m,
4 H, RCHAr2), 2.34 (m, 8 H, CHCH2R), 1.28 (m, 72 H, CH2),
1
0.88 (m, 12 H, CH3) ppm. H NMR (300 MHz, CD2Cl2): δ = 8.64
Ethynylpyridine Monophosphonate Cavitand 1: PdCl2(PPh3)2 (5 mg,
0.007 mmol), CuI (2 mg, 0.0115 mmol), PPh3 (48 mg, 0.345 mmol)
and ethynylpyridine (3 mg, 0.0115 mmol) were added under nitro-
gen to a solution of the cavitand 11i (320 mg, 0.23 mmol) dissolved
in dry THF/triethylamine (1:1, 20 mL). The solution was stirred
at 50 °C for 48 h and then filtered to remove metallic Pd. After
evaporation of the solvent, the crude product was purified by col-
umn chromatography on silica gel with hexane/CH2Cl2/EtOH
(5:4.5:0.5, v/v) as eluent to give 1 as a solid in 50% yield (0.156 g,
0.1143 mmol). 1H NMR (300 MHz, CDCl3): δ = 8.63 (brd, XXЈ
part of an AAЈXXЈ system, 2 H, PyHo), 8.07–8.00 [dd, 3J = 8.4,
3J(P,H) = 14.1 Hz, AAЈ part of an AAЈBBЈ system, 2 H, POArHo],
7.81–7.77 (m, BBЈ part of an AAЈBBЈ system, 2 H, POArHm), 7.51
(brd, AAЈ part of an AAЈXXЈ system, 2 H, PyHm), 7.14 (s, 2 H,
3
(m, AAЈ part of an AAЈXXЈ system, 4 H, PyHo), 8.21 [dd, J(P,H)
= 15.0, 3J = 7.0 Hz, 4 H, POArH], 7.79 (d, AAЈ part of an AAЈBBЈ
system, 4 H, ArHPy), 7.72 (m, BBЈ part of an AAЈBBЈ system, 6
H, ArHPy, POArH), 7.60 (m, XXЈ part of an AAЈXXЈ system, 8
H, PHm, POArH), 7.32 (s, 4 H, ArHdown), 6.76 [s, 4J(P,H) = 2.0 Hz,
4 H, ArHup], 5.51 (s, 2 H, CH), 4.87 (m, 4 H, RCHAr2), 2.42 (m,
4 H, CHCH2R), 2.32 (m, 4 H, CHCH2R), 1.27 (m, 72 H, CH2),
0.87 (m, 12 H, CH3) ppm. 31P NMR (162 MHz, CDCl3): δ = 75.6
(s, 2 P) ppm. MS (ESI): m/z (%): calcd. for C108H132N2O8P2S2 [M]
1712.3; found 1713.0 [M + H]+; acetone/CH2Cl2 with a drop of
+
HCOOH. HR-ESI-MS: m/z calcd. for C108H133N2O8P2S2 [M +
H]+ 1711.89701; found 1711.89964.
Dithiophosphonate Cavitand 13bout: A mixture of the resorcinarene
12b (98 mg, 0.11 mmol), K2CO3 (155 mg, 1.12 mmol) and 4-(α,α-
dibromo-p-tolyl)pyridine (147 mg, 0.45 mmol) in dry DMF
(10 mL) was stirred in a sealed tube at 85 °C for 19 h. The reaction
mixture was then allowed to cool and poured into water, and the
solid formed was filtered and dried. The crude product was purified
by column chromatography on silica gel with CH2Cl2/ethyl acetate
(8:2, v/v) as eluent to give 13bout in a 45% yield (61 mg,
0.05 mmol). 1H NMR (300 MHz, CDCl3): δ = 8.65 (d, AAЈ part
4
ArHdown), 7.08 (s, 2 H, ArHdown), 6.66 [s, J(P,H) = 1.4 Hz, 2 H,
ArHup], 6.52 (s, 2 H, ArHup), 5.75 (d, 2J = 7.3 Hz, 1 H, CHout),
5.64 (d, 2J = 7.3 Hz, 2 H, CHout), 4.75 (t, 3J = 7.9 Hz, 2 H,
RCHAr2), 4.61–4.69 (m, 3 H, CHin, 2 H, RCHAr2), 2.16–2.33 (m,
8 H, CHCH2R), 1.20–1.40 (m, 72 H, CH2), 0.86 (t, 3J = 6.9 Hz,
12 H, CH3) ppm. 31P NMR (162 MHz, CDCl3): δ = 6.43 (s, 1 P,
POAr) ppm. MS (ESI): m/z (%) calcd. for C88H118NO9P [M]
1364.9, calcd. for [M
+
H]+ 1365.9; found 1366.4 (100).
C88H118NO9P (1364.88): calcd. C 77.44, H 8.71, N 1.03; found C
77.24, H 8.41, N 1.42.
3
3
of an AAЈXXЈ system, 4 H, PyHo), 8.20 [dd, J(P,H) = 15.0, J =
7.0 Hz, 4 H, POArHo], 7.79 (d, AAЈ part of an AAЈBBЈ system, 4
Re Ditopic Complex 4: The cavitand 1 (26.7 mg, 0.0195 mmol) was H, ArHPy),7.65 (m, BBЈ part of an AAЈBBЈ system, 6 H, ArHPy,
added under argon to
a
solution of Re(CO)5Br (3.8 mg,
POArH), 7.55 (m, XXЈ part of an AAЈXXЈ system, 8 H, ArHPy,
POArH), 7.30 (s, 4 H, ArHdown), 6.78 (s, 4 H, ArHup), 5.68 (s, 2
H, RCHArPy), 4.81 (t, 3J = 8.1 Hz, 2 H, RCHAr2), 4.74 (brt, 2 H,
RCHAr2), 2.38 (m, 8 H, CH2), 1.08 (m, 12 H, CH3) ppm. 31P NMR
0.00928 mmol) in dry CHCl3 (10 mL). The solution was heated at
reflux for 48 h. After evaporation of the solvent, the crude product
was purified by preparative TLC on silica gel with CH2Cl2/EtOH/
Eur. J. Org. Chem. 2011, 2629–2642
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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