L. Monnereau, D. Sémeril, D. Matt
FULL PAPER
3
CH), 6.21 (d, J = 7.6 Hz, 4 H, arom. CH), 5.29 (s, 4 H, CH2Ph), 25,26,27,28-Tetrabenzyloxy-5,17-bis(diphenylphosphinoyl)calix[4]-
arene (7): H2O2 (30% in water, 4 mL, 5.0 mmol) was added to a
8 H, ArCH2Ar), 3.83 [sept, J = 6.8 Hz, 4 H, CH(CH3)2], 1.12 [d, solution of 25,26,27,28-tetrabenzyloxy-5,17-bis(diphenylphos-
4.42 (s, 4 H, CH2Ph), 4.25 and 2.78 (AB spin system, 2J = 13.6 Hz,
3
3J = 6.8 Hz, 24 H, CH(CH3)2] ppm. 13C {1H} NMR (75 MHz,
CDCl3): δ = 157.65, 153.86 (2 s, arom. Cquat.–O), 142.56–118.62
(arom. C), 76.77 (s, OCH2Ph), 74.40 (s, OCH2Ph), 30.53 (s, Ar-
phanyl)calix[4]arene (1, 0.576 g, 0.5 mmol) in CH2Cl2 (10 mL). The
resulting solution was stirred at room temperature for 2 h. The mix-
ture was treated with a mixture of CH2Cl2 (10 mL) and water
CH2Ar), 27.49 [s, CH(CH3)2], 22.78 [s, CH(CH3)2] ppm. 31P {1H} (20 mL). After extraction of the aqueous layer with CH2Cl2
NMR (121 MHz, C D ): δ = –3.3 (s, PPh ) ppm. IR: ν = 1329 (2ϫ10 mL), the organic phases were combined. The resulting solu-
˜
6
6
2
(P=N) cm–1. MS (MALDI-TOF): m/z = 1503.69 [M + H]+ (ex-
pected isotopic profile). C104H100N2O4P2 (1503.86): calcd. C 83.06,
H 6.70, N 1.82; found C 82.82, H 6.54, N 1.80.
tion was washed with water (2ϫ10 mL), dried with Na2SO4 and
concentrated under reduced pressure to afford the bis(phos-
phane oxide) 7 as a white solid in quantitative yield. 1H NMR
(300 MHz, CDCl3): δ = 7.58–7.34 (20 H, arom. CH), 7.24–6.96 (24
H, arom. CH), 6.16 (t, J = 7.5 Hz, 2 H, arom. CH), 5.90 (d, J =
7.5 Hz, 4 H, arom. CH), 5.12 (s, 4 H, CH2Ph), 4.56 (s, 4 H,
CH2Ph), 4.12 and 2.82 (AB spin system, 2J = 13.8 Hz, 8 H, Ar-
CH2Ar) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 158.97 (d,
4JP,C = 2.8 Hz, arom. Cquart.–O), 154.29 (s, arom. Cquart.–O),
137.64–122.21 (arom. C), 77.12 (s, OCH2Ph), 75.03 (s, OCH2Ph),
30.89 (s, ArCH2Ar) ppm. 31P {1H} NMR (121 MHz, CDCl3): δ =
31.0 (s, O=PPh2) ppm. C80H66O6P2 (1185.32): calcd. C 81.06, H
5.61; found C 80.89, H 5.72.
25,26,27,28-Tetrabenzyloxy-5,17-bis(4-butylphenyliminodiphenyl-
3
3
1
phosphoranyl)calix[4]arene (4): H NMR (300 MHz, C6D6): δ =
8.04–7.98 (8 H, arom. CH), 7.64 (d, 3J = 11.5 Hz, 4 H, arom. CH),
3
3
7.37 (d, J = 8.0 Hz, 4 H, arom. CH), 7.29 (d, J = 7.0 Hz, 4 H,
arom. CH), 7.19–6.96 (32 H, arom. CH), 6.45 (t, 3J = 7.6 Hz, 2 H,
arom. CH), 6.18 (d, 3J = 7.6 Hz, 4 H, arom. CH), 5.19 (s, 4 H,
2
CH2Ph), 4.45 (s, 4 H, CH2Ph), 4.20 and 2.70 (AB spin system, J
3
= 13.7 Hz, 8 H, ArCH2Ar), 2.60 (t, J = 6.5 Hz, 4 H, C6H4CH2),
1.62 (quint, 3J = 6.5 Hz, 4 H, C6H4CH2CH2), 1.33 (sext, 3J =
3
6.4 Hz, 4 H, CH2CH3), 0.86 (t, J = 6.4 Hz, 6 H, CH2CH3) ppm.
13C {1H} NMR (75 MHz, C6D6): δ = 159.74 (d, JP,C = 3.1 Hz,
Digold Complex 8: A solution of [AuCl(THT)] (0.045 g, 0.14 mmol)
4
arom. Cquart.–O), 155.08 (s, arom. Cquart.–O), 150.22–123.28 (arom. in THF (5 mL) was added to a stirred solution of 2 (0.100 g,
C), 77.63 (s, OCH2Ph), 75.80 (s, OCH2Ph), 35.60 (s, C6H4CH2), 0.07 mmol) in CH2Cl2 (15 mL). After 5 h, the solution was concen-
34.63 (s, C6H4CH2CH2), 31.66 (s, ArCH2Ar), 22.79 (s, CH2CH3),
trated to ca. 1 mL. Addition of hexane afforded 8 as a white solid
14.31 (s, CH2CH3) ppm. 31P {1H} NMR (121 MHz, C6D6): δ = (0.112 g, 86%). 1H NMR (300 MHz, C6D6): δ = 7.93–7.72 (8 H,
–0.4 (s, PPh ) ppm. IR: ν = 1325 (P=N) cm–1. MS (MALDI-TOF):
arom. CH), 7.54–7.42 (4 H, arom. CH), 7.32 (d, J = 6.3 Hz, 4 H,
arom. CH), 7.18–6.96 (30 H, arom. CH), 6.71 (s, 4 H, arom. CH),
6.22–6.09 (4 H, arom. CH), 5.25 and 5.21 (AB spin system, 2J =
13.1 Hz, 4 H, CH2Ph), 4.43 (s, 4 H, CH2Ph), 4.20 and 2.74 (AB
spin system, 2J = 13.8 Hz, 8 H, ArCH2Ar), 2.33 (s, 12 H, o-CH3
of mesityl), 2.17 (s, 6 H, p-CH3 of mesityl) ppm. 13C {1H} NMR
3
˜
2
m/z = 1447.59 [M + H]+ (expected isotopic profile). C100H92N2O4P2
(1447.76): calcd. C 82.96, H 6.40, N 1.93; found C 82.83, H 6.25,
N 1.92.
25,26,27,28-Tetrabenzyloxy-5,17-bis(2-methoxyphenyldiphenyl-
1
phosphoranyl)calix[4]arene (5): H NMR (300 MHz, C6D6): δ =
4
(75 MHz, C6D6): δ = 159.85 (d, JP,C = 3.7 Hz, arom. Cquat.–O),
8.04–7.98 (8 H, arom. CH), 7.63 (d, 3J = 11.8 Hz, 4 H, arom. CH),
155.36 (s, arom. Cquat.–O), 141.59–124.31 (arom. C), 78.07 (s,
OCH2Ph), 76.06 (s, OCH2Ph), 32.31 (s, ArCH2Ar), 23.40
(s, o-CH3 of mesityl), 21.54 (s, p-CH3 of mesityl) ppm. 31P {1H}
3
3
7.50 (d, J = 7.6 Hz, 2 H, arom. CH), 7.29 (d, J = 7.3 Hz, 4 H,
arom. CH), 7.20–6.80 (34 H, arom. CH), 6.38 (t, 3J = 7.5 Hz, 2 H,
arom. CH), 6.15 (d, 3J = 7.5 Hz, 4 H, arom. CH), 5.19 (s, 4 H,
NMR (121 MHz, C6D6):
δ
=
28.6 (s, PPh2) ppm.
2
CH2Ph), 4.46 (s, 4 H, CH2Ph), 4.21 and 2.72 (AB spin system, J
C98H88Au2Cl2N2O4P2·C6H14 (1884.54 + 86.17): calcd. C 63.38, H
5.22, N 1.42; found C 63.12, H 5.36, N 1.67.
= 13.6 Hz, 8 H, ArCH2Ar), 3.32 (s, 6 H, CH3OC6H4) ppm. 13C
{1H} NMR (75 MHz, C6D6): δ = 159.17 (d, JP,C = 3.7 Hz, arom.
4
Cquart.–O), 155.08 (s, arom. Cquart.–O), 153.58–112.20 (arom. C), Reaction of 6 with [PdCl2(CH3CN)2]: A solution of 6 (0.150 g,
77.63 (s, OCH2Ph), 75.74 (s, OCH2Ph), 54.84 (s, CH3OC6H4), 31.70
0.011 mmol) in CH2Cl2 (100 mL) was added slowly to a solution
of [PdCl2(CH3CN)2] (0.028 mg, 0.011 mmol) in CH2Cl2 (200 mL).
The resulting solution was stirred overnight and then concentrated
to ca. 5 mL. Addition of hexane (100 mL) afforded a brown pre-
cipitate, which turned out to contain several complexes that could
not be separated. MS (ESI-TOF, crude reaction mixture): m/z (%)
= 1573.41 (1) ([PdCl2(6) + H]+ requires 1573.40; expected isotopic
profile; see Scheme S2 in the Supporting Information).
(s, ArCH2Ar) ppm. 31P {1H} NMR (121 MHz, C6D6): δ = 0.5 (s,
PPh ) ppm. IR: ν = 1326 (P=N) cm–1. MS (MALDI-TOF): m/z =
˜
2
1395.50 [M + H]+ (expected isotopic profile). C94H80N2O6P2
(1395.60): calcd. C 80.90, H 5.78, N 2.01; found C 80.79, H 5.90,
N 1.81.
25,26,27,28-Tetrabenzyloxy-5,17-bis(4-methoxyphenyliminodi-
phenylphosphoranyl)calix[4]arene (6): 1H NMR (300 MHz, C6D6):
3
δ = 8.04–7.98 (8 H, arom. CH of PPh2), 7.63 (d, J = 11.7 Hz, 4 Silver Complex 9: A solution of AgBF4 (0.028 g, 0.14 mmol) in
3
3
H, arom. CH), 7.30 (d, J = 6.3 Hz, 4 H, arom. CH), 7.28 (d, J =
6.3 Hz, 4 H, arom. CH), 7.20–6.91 (32 H, arom. CH), 6.44 (t, 3J =
7.6 Hz, 2 H, arom. CH), 6.14 (d, 3J = 7.6 Hz, 4 H, arom. CH),
5.19 (s, 4 H, CH2Ph), 4.45 (s, 4 H, CH2Ph), 4.21 and 2.71 (AB spin
THF (10 mL) was added to a stirred solution of 6 (0.200 g,
0.14 mmol) in THF (40 mL). After 2 h, the solution was concen-
trated to ca. 1 mL. Addition of hexane afforded 9 as a white solid
(0.208 g, 92%). 1H NMR (300 MHz, CD2Cl2): δ = 7.73–7.15 (45
system, 2J = 13.5 Hz, 8 H, ArCH2Ar), 3.46 (s, 6 H, CH3OC6H4) H, arom. CH), 7.01–6.96 (6 H, arom. CH), 6.92 (d, J = 12.4 Hz,
3
4
3
ppm. 13C {1H} NMR (75 MHz, C6D6): δ = 159.33 (d, JP, C
=
2 H, arom. CH), 6.79 (d, J = 7.2 Hz, 2 H, arom. CH), 6.58–6.52
3.1 Hz, arom. Cquart.–O), 154.64 (s, arom. Cquart.–O), 152.45–114.63 (4 H, arom. CH), 6.54 (s, 4 H, CH2Ph), 4.88 (s, 4 H, CH2Ph), 4.22
2
(arom. C), 77.24 (s, OCH2Ph), 75.41 (s, OCH2Ph), 54.93 (s,
CH3OC6H4), 31.29 (s, ArCH2Ar) ppm. 31P {1H} NMR (121 MHz,
and 2.89 (AB spin system, 8 H, ArCH2Ar, J = 13.4 Hz), 3.70 (s,
6 H, CH3OC6H4) ppm. 13C {1H} NMR (75 MHz, CD2Cl2): δ =
159.68 (s, arom. Cquart.–O), 155.50 (s, arom. Cquart.–O), 152.50–
114.30 (arom. C), 78.49 (s, OCH2Ph), 76.12 (s, OCH2Ph), 55.87 (s,
CH3OC6H4), 31.89 (s, ArCH2Ar) ppm. 31P {1H} NMR (121 MHz,
CD2Cl2): δ = 24.8 [d, PPh2, 2J(P107,Ag) ≈ 2J(P109,Ag) = 7.7 Hz].
C D ): δ = –0.5 (s, PPh ) ppm. IR: ν = 1328 (P=N) cm–1. MS
˜
6
6
2
(MALDI-TOF): m/z = 1395.54 [M + H]+ (expected isotopic pro-
file). C94H80N2O6P2 (1395.60): calcd. C 80.90, H 5.78, N 2.01;
found C 80.96, H 5.95, N 1.88.
2790
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Eur. J. Org. Chem. 2012, 2786–2791