Page 19 of 23
The Journal of Organic Chemistry
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MgSO4, and concentrated in vacuo to give [2]rotaxane a2A (38 mg, 0.0206 mmol, 96%) as a colorless film. 1H
NMR (400 MHz, CDCl3) δ 7.81 - 7.79 (m, 2H), 7.72 (m, 2H), 7.61-7.41 (m, 11H), 7.31 (d, J = 8.0 Hz, 6H), 7.23
(d, J = 8.2 Hz, 6H), 6.99 (s, 4H), 5.63 (s, 2H), 5.54-5.43 (m, 2H), 4.30-4.15 (m, 4H), 4.14-4.03 (m, 2H), 3.23-3.10
(m, 2H), 2.99-2.78 (m, 4H), 2.65-2.53 (m, 6H), 2.23 (s, 4H), 1.58-1.42 (m, 6H), 1.42-1.14 (m, 75H), 1.14-0.65
(m, 24H). 13C{1H} NMR (100 MHz, CDCl3 δ 164.9, 164.7, 151.3, 151.3, 150.9, 150.8, 149.5, 149.4, 149.3, 148.8,
143.0, 142.6, 142.5, 142.4, 137.3, 128.8, 128.3, 126.8, 125.8, 125.7, 125.5, 124.9, 124.4, 124.4, 121.1, 117.0,
117.0, 69.6, 69.3, 67.0, 64.3, 54.2, 54.1, 54.0, 53.3, 48.1, 40.7, 34.5, 34.2, 33.9, 31.6, 31.2, 31.0, 30.4, 29.6,
29.3, 29.1, 29.0, 29.0, 24.7, 22.6. MS (FD+) m/z calcd for C122H164N6O8 (M•+) 1841.3, found 1841.3.
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Prerotaxane A23B
Compound A2 (54.5 mg, 0.0411 mmol, 1.0 equiv), B3 (110 mg, 2 equiv), and TBTA (15 mg, 0.028 mmol, 0.68
equiv) were dissolved in dry CH2Cl2 (3 mL) and the solution was degassed with five vacuum/N2 cycles.
Cu(CH3CN)4BF4 (13 mg, 0.041 mmol, 1.0 equiv) was added and the reaction was stirred for 18h at room
temperature under N2 atmosphere. The mixture was concentrated in vacuo and purified by column
chromatography (PE/EtOAc 8:1 5:1 2:1) to give A23B (60.5 mg, 0.0228 mmol, 55%) as a glass. 1H NMR
(400 MHz, CDCl3) δ 8.02– 7.31 (m, 26H), 7.24-7.18 (m, 2H), 7.18-7.06 (m, 8H), 7.04-6.89 (m, 1H), 5.54-5.49
(m, J = 2H), 4.88-4.69 (m, 2H), 4.64-4.44 (m, 2H), 4.27 (t, J = 4.9 Hz, 12H), 4.18 (br m, 6H), 2.91 (br m, 4H),
2.53 (br m, 18H), 1.49 (br m, 8H), 1.39 (br m, 18H), 1.29 (br m, 72H), 1.12 (br m, 18H), 0.91 (br m, 32H). 13C{1H}
NMR (125 MHz, CDCl3) δ 176.4, 142.5, 138.0, 134.4, 128.4, 127.9, 126.9, 126.1, 125.8, 125.7, 125.2, 125.1,
123.2, 79.5, 70.6, 69.8, 69.4, 63.0, 47.2, 46.8, 34.6, 34.4, 34.1, 31.9, 31.7, 31.5, 31.4, 31.4, 31.4, 30.5, 30.2,
29.7, 29.7, 29.6, 29.4, 29.1, 28.3, 25.5, 23.1, 22.7, 22.6, 21.7, 21.4, 19.3, 19.2, 19.0, 19.0, 17.8, 14.1, 14.0,
11.8. HRMS (ESI+) m/z calcd for C175H233N9O12 [M + 2H)]2+ 1326.8961, found 1326.8928.
[3]Rotaxane A23B (tetra methyl ester)
Prerotaxane A23B (30 mg, 0.0113 mmol) was dissolved in a mixture of dioxane (4 mL) and methanol (1 mL),
a solution of NaOH (40 mg) in water (0.5 ml) was added and the reaction was stirred at 50 C during 72 h.
The mixture was subsequently diluted with EtOAc (10 mL) and a saturated KHSO4 solution (10 mL). The
organic layer was washed with brine (5 mL), dried over Na2SO4, and concentrated in vacuo to give the diacid,
which was immediately converted to the diester. A solution of HCl in MeOH (prepared from 8 ml MeOH and
1.5 ml acetyl chloride at 50 C) was added and the solution was stirred at 50 C during 5 h. The reaction
mixture was concentrated in vacuo, the residue was co-evaporated with MeOH (3x 5 ml) and purified by flash
chromatography (PE/EtOAc 3:1 and 2:1) to give [3]rotaxane A23B (16.1 mg, 0.00579 mmol, 51%) as a glass.1H
NMR (400 MHz, CDCl3) δ 8.27 (s, 1H), 8.06-7.96 (m, 2H), 7.77 (s, 1H), 7.73 (s, 1H), 7.51 (d, J = 8.3 Hz, 4H), 7.49-
7.44 (m, 7H), 7.44-7.41 (m, 2H), 7.41-7.30 (m, 10H), 7.11 (s, 2H), 7.01 (s, 4H), 6.99 (s, 4H), 5.45 (s, 2H), 4.77
(t, J = 6.8 Hz, 2H), 4.53 (t, J = 6.8 Hz, 2H), 4.17-3.94 (m, 8H), 3.84 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H),
2.98-2.85 (m, 4H), 2.78-2.48 (m, 18H), 2.41-2.31 (m, 2H), 2.27-2.11 (m, 4H), 1.62-1.46 (m, 20H), 1.38 (s, 18H),
1.36 (s, 18H), 1.32 (s, 18H), 1.30 (s, 20H), 1.27-1.13 (m, 16H), 1.13-0.82 (m, 42H). 13C{1H} NMR (100 MHz,
CDCl3) δ 165.8, 165.7, 165.3, 165.1, 151.8, 151.7, 150.7, 150.2, 149.8, 149.7, 147.5, 147.4, 146.9, 142.5, 142.3,
142.0, 137.8, 137.4, 135.6, 130.8, 129.1, 128.9, 126.8, 125.9, 125.7, 125.6, 125.4, 124.3, 124.2, 124.1, 124.0,
123.2, 121.7, 121.3, 121.1, 116.7, 116.6, 77.2, 77.1, 76.9, 76.6, 68.8, 66.0, 65.6, 54.0, 52.4, 52.2, 52.1, 46.9,
46.7, 34.5, 34.4, 33.9, 33.8, 31.8, 31.6, 31.3, 31.2, 31.1, 30.5, 30.4, 29.8, 29.7, 29.6, 29.5, 29.4, 29.3, 29.2,
29.0, 28.9, 22.6, 22.0, 21.9, 14.0. HRMS (ESI+) m/z calcd for C179H247N9O16 (M•+) 2779.8819, found 2779.8762.
Prerotaxane a2L2a
Prerotaxane 1 (110 mg, 0.0779 mmol, 2.2 equiv), linker L (6.67 mg, 0.0354 mmol, 1 eq) and TBTA (3.76 mg,
0.00708 mmol, 0.2 equiv) were dissolved in 10 mL dry DCM and then Cu(CH3CN)4BF4 (2.23 mg, 0.00708 mmol,
0.2 equiv) was added to the solution. The solution was stirred at room temperature under N2 atmosphere
overnight. Subsequently the solution was concentrated in vacuo and the crude product was purified by
column chromatography to yield prerotaxane a2L2a as a white film (0.0790 g, 0.0263 mmol, 74%). 1H NMR
(400 MHz, CDCl3) δ 7.91-7.79 (m, 2H), 7.77-7.63 (m, 2H), 7.31 (d, J = 8.3 Hz, 12H), 7.24 (d, J = 8.5 Hz, 12H),
7.21-6.89 (m, 16H), 5.47-5.27 (m, 4H), 4.32-4.12 (m, 8H), 4.12-3.93 (m, 4H), 3.16 (t, J = 8.3 Hz, 4H), 3.05-2.82
(m, 8H), 2.79-2.12 (m, 24H), 1.59 (br m, 16H), 1.34 (m, 110H), 1.06 (br m, 44H). 13C{1H} NMR (100 MHz, CDCl3)
δ 148.7, 143.1, 134.4, 128.3, 124.8, 68.6, 54.0, 53.3, 47.8, 40.7, 34.3, 34.2, 31.4, 31.2, 30.5, 30.1, 29.8, 29.6,
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