The Journal of Organic Chemistry
Page 14 of 16
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MHz, CDCl3) δ 8.32 (dd, J = 1.6, 1.6 Hz, 1H), 8.14 (dd, J = 1.6, 1.6 Hz, 1H), 8.03 (dd, J = 1.6, 1.6 Hz, 1H), 7.14 (dd, J = 8.1, 7.7 Hz, 1H), 6.93
(ddd, J = 7.7, 1.6, 1.0 Hz, 1H), 6.84 (dd, J = 2.4, 1.6 Hz, 1H), 6.69 (ddd, J = 8.1, 2.4, 1.0 Hz, 1H), 4.53 – 4.47 (m, 2H), 3.87 – 3.81 (m, 2H),
3.72 (br s, 2NH), 3.72– 3.67 (m, 2H), 3.60 – 3.55 (m, 2H), 3.40 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ 164.8, 146.6, 144.3, 138.1,
132.2, 132.1, 129.6, 125.9, 123.3, 122.4, 118.0, 116.1, 93.4, 92.2,86.3, 72.1, 70.8, 69.3, 64.8, 59.4. HRMS (ESI-TOF) m/z: [M+H]+ calcd
for C20H21INO4 466.0510; Found 466.0537.
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Duplex B•B-A•A. A 0.1 M solution of dianiline A•A (2 mg) in benzene was added to a 0.1 M solution of dialdehyde B•B (2
mg) in benzene. TFA was then added (0.1 uL), and the solution was placed in a freezer. After sitting for three days, colorless, needle-
like crystals had formed. The benzene supernatant was carefully removed with a pipette leaving pure white crystals of B•B-A•A (4
mg, 100%). 1H NMR (500 MHz, CDCl3) δ 8.58 (s, 2H), 8.18 (d, J = 1.6 Hz, 2H), 8.17 (d, J = 1.6 Hz, 2H), 8.13 (dd, J = 1.8, 1.6 Hz, 2H), 7.938
(ddd, J = 7.7, 1.7, 1.4, 2H), 7.933 (t, J = 1.6 Hz, 2H), 7.91 (t, J = 1.6 Hz, 1H), 7.66 (ddd, J = 7.7, 1.6, 1.2 Hz, 2H), 7.52 (dd, J = 2.1, 1.6 Hz,
2H), 7.50 (dd, J = 7.7, 7.7 Hz, 2H), 7.45 (ddd, J = 7.5, 1.6, 1.5 Hz, 2H), 7.42 (dd, J = 7.5, 7.5 Hz, 2H), 7.34 (ddd, J = 7.5, 2.1, 1.5 Hz, 2H),
4.58 – 4.51 (overlap, 4H), 3.92 – 3.86 (overlap, 4H), 3.77 – 3.70 (overlap, 4H), 3.63 – 3.59 (overlap, 4H), 3.42 (s, 6H); 13C{1H} NMR
(125 MHz, CDCl3) δ 165.5, 165.4, 159.3 (2C), 151.0 (2C), 139.4, 139.2, 136.6 (2C), 134.3 (2C), 133.0 (2C), 132.24 (2C), 132.22 (2C),
131.15, 131.09, 129.8 (2C), 129.6 (2C), 129.3 (2C), 128.8 (2C), 124.9 (2C), 124.2 (2C), 124.1 (2C), 123.8 (2C), 123.6 (2C), 122.2 (2C),
90.8 (2C), 90.5 (2C), 88.6 (2C), 88.2 (2C), 72.2 (2C), 70.8 (2C), 69.4 (2C), 64.75, 64.73, 59.4. HRMS (MALDI-TOF) m/z: [M+H]+ calcd
for C58H47N2O8 899.3333; Found 899.8992. The structure of B•B-A•A was further confirmed by X-Ray crystallography (see
supporting information).
Duplex B•A-A•B. Prepared according to the general Sonogashira cross coupling procedure: aryliodide 2 (45 mg, 0.1 mmol) was
reacted with 3-ethynylbenzaldehyde B (14 mg, 0.11 mmol) in the presence of Pd(PPh3)4 (12 mg, 0.01 mmol), CuI (4 mg, 0.02 mmol),
and TEA (0.7 mL) in DMF (1 mL) at rt for 16 h. CombiFlash silica gel purification (gradient of 0-100% EtOAc in hexanes) gave a
mixture of A•B and B•A-A•B. The fractions containing A•B and B•A-A•B were combined, heated to 60 °C in an oil bath for 1 h, then
concentrated. The residue was precipitated from a mixture of chloroform and benzene (1:4 respectively) to give pure B•A-A•B (10
mg, 22%) as a white solid. 1H NMR (500 MHz, CDCl3) δ 8.58 (s, 2H), 8.18 (t, J = 1.6 Hz, 2H), 8.17 (t, J = 1.6 Hz, 2H), 8.11 (t, J = 1.7 Hz,
2H), 7.95 (ddd, J = 7.8, 1.7, 1.2 Hz, 2H), 7.92 (t, J = 1.6 Hz, 2H), 7.66 (ddd, J = 7.6, 1.6, 1.2 Hz, 2H), 7.51 (dd, J = 2.1, 1.6 Hz, 3H), 7.49 (dd,
J = 7.8, 7.6 Hz, 2H), 7.45 (ddd, J = 7.6, 1.6, 1.4 Hz, 2H), 7.42 (dd, J = 7.6, 7.6 Hz, 2H), 7.35 (ddd, J = 7.6, 2.1, 1.4 Hz, 2H), 4.57 – 4.53 (m,
4H), 3.91 –3.87 (m, 4H), 3.76 – 3.71 (m, 4H), 3.63 – 3.59 (m, 4H), 3.42 (s, 6H); 13C{1H} NMR (125 MHz, CDCl3) δ 165.5 (2C), 159.4 (2C),
151.0 (2C), 139.3 (2C), 136.6 (2C), 134.4 (2C), 133.1 (2C), 132.3 (2C), 132.2 (2C), 131.1 (2C), 129.8 (2C), 129.6 (2C), 129.3 (2C), 128.7
(2C), 124.8 (2C), 124.3 (2C), 124.1 (2C), 123.8 (2C), 123.6 (2C), 122.4 (2C), 90.9 (2C), 90.4 (2C), 88.7 (2C), 88.1 (2C), 72.2 (2C), 70.8
(2C), 69.4 (2C), 64.7 (2C), 59.4 (2C). HRMS (MALDI-TOF) m/z: [M+H]+ calcd for C58H47N2O8 899.3333; Found 899.4021.
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