Synthesis of Self-Folded Molecular
Rotors Controlled by Edge-to-Face CH/π Aromatic
Interactions

Yitao Li; Yanping Zhu; Jing Qin; Huizhen Guo; Lin Li; Anxin Wu

doi:10.1055/s-0029-1217528

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Synlett 2009(12): 2028-2034
DOI: 10.1055/s-0029-1217528

LETTER

Synthesis of Self-Folded Molecular Rotors Controlled by Edge-to-Face CH/π Aromatic Interactions

Yitao Li, Yanping Zhu, Jing Qin, Huizhen Guo, Lin Li, Anxin Wu*
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079,P. R. of China
e-Mail: chwuax@mail.ccnu.edu.cn;

Further Information

Publication History

Received 25 March 2009
Publication Date:
01 July 2009 (online)

Abstract
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Abstract

A series of novel self-folded molecular rotors were synthesized and characterized by ^¹H NMR, ^¹³C NMR, HRMS, and IR data. All but two compounds were also studied by X-ray crystallography.

Key words

self-folded - molecular rotors - CH/p interactions - molecular clips - diethoxycarbonyl glycoluril

Supporting Information

References and Notes

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9

Special Issue of Scientific American: Nanotech: The Science of Small Gets Down to Business, September 2001.

17

Synthesis of 7; General Procedure
DMF and the aliphatic amines had to be freshly distilled or recrystallized under nitrogen. Compounds 4 and 5a-g were synthesized as reported previously.^¹5 The intermediates 5h and 5i were then produced from 5g through Sonogashira cross-coupling reactions. Thus, a suspension of 5 (5 mmol) in 37% aq formaldehyde (3.5 mL) and DMF (30 mL) was brought to reflux under magnetic stirring. A solution of aliphatic amine (5 mmol) in DMF (20 mL) was added slowly, dropwise (over 1 h) to the mixture. Refluxing was continued and the reaction was monitored by TLC. Upon completion, the solvent was removed under reduced pressure and the products were separated by column chromatography on silica gel (CHCl₃-MeOH) to give compound 7 as a solid.

18

Compound 7a: Yield: 58%; white solid; mp 159-160 ˚C; IR (KBr): 2960, 2923, 2852, 1737, 1635, 1377, 1267, 752, 722 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.50-7.47 (m, 2 H), 7.30-7.19 (m, 5 H), 6.88-6.85 (m, 2 H), 4.86 (d, J = 15.6 Hz, 2 H), 4.65 (d, J = 15.2 Hz, 4 H), 4.39-4.25 (m, 6 H), 2.88 (s, 2 H), 1.38-1.25 (m, 6 H); ^¹³C NMR (CDCl₃,100 MHz): δ = 165.9, 165.6, 156.9, 136.2, 130.0, 129.0, 128.0, 127.4, 114.2, 80.3, 75.9, 63.3, 63.2, 59.8, 53.7, 45.5, 14.0, 13.9; HRMS: m/z [M + H]⁺ calcd for C₂₇H₂₉N₅O₆: 519.2118; found: 520.2191.
Compound 7b: Yield: 45%; white solid; mp 160-161 ˚C; IR (KBr): 3064, 2973, 2938, 1738, 1718, 1452, 1414, 1263, 752 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.24-7.18 (m, 5 H), 6.85-6.82 (m, 2 H), 4.77 (d, J = 15.6 Hz, 2 H), 4.62 (d, J = 13.6 Hz, 2 H), 4.57 (d, J = 15.6 Hz, 2 H), 4.37-4.24 (m, 6 H), 2.87 (s, 2 H), 2.22 (s, 6 H), 1.36-1.28 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.9, 165.7, 156.9, 136.5, 136.0, 133.4, 131.2, 128.9, 127.9, 127.2, 80.4, 75.9, 63.1, 63.0, 59.8, 53.7, 45.0, 19.1, 13.9, 13.8; HRMS: m/z [M + H]⁺ calcd for C₂₉H₃₃N₅O₆: 547.2431; found: 548.2504.
Compound 7c: Yield: 67%; white solid; mp 228-229 ˚C; IR (KBr): 3069, 2957, 2936, 2852, 1762, 1718, 1465, 1417, 1282, 741 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.21-7.19 (m, 3 H), 7.00-6.91 (m, 4 H), 4.78 (d, J = 16.0 Hz, 2 H), 4.68 (d, J = 14.0 Hz, 2 H), 4.61 (d, J = 16.0 Hz, 2 H), 4.40-4.28 (m, 6 H), 3.91 (s, 6 H), 2.94 (s, 2 H), 1.38-1.30 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.9, 165.7, 156.9, 147.7, 136.3, 128.9, 128.7, 127.9, 127.2, 113.3, 80.3, 76.0, 63.2, 63.1, 59.8, 56.0, 53.6, 45.1, 13.9, 13.8; HRMS: m/z
[M + H]⁺ calcd for C₂₉H₃₃N₅O₈: 579.2329; found: 580.2402.
Compound 7d: Yield: 45%; yellow solid; mp 247-248 ˚C; IR (KBr): 3061, 2927, 2852, 1761, 1743, 1721, 1457, 1420, 1251, 752 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.42-7.21 (m, 5 H), 6.95 (d, J = 6.8 Hz, 2 H), 5.67 (d, J = 16.0 Hz, 2 H), 4.68 (d, J = 13.6 Hz, 2 H), 4.57 (d, J = 16.0 Hz, 2 H), 4.40-4.26 (m, 6 H), 3.00 (s, 2 H), 1.38-1.30 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.7, 165.5, 156.7, 137.8, 136.2, 133.9, 129.1, 128.1, 127.4, 124.2, 79.0, 76.4, 63.4, 63.2, 59.9, 54.0, 44.9, 14.0, 13.9; HRMS: m/z [M + H]⁺ calcd for C₂₇H₂₇Br₂N₅O₆: 675.0328; found: 676.0401. Compound 7e: Yield: 50%; white solid; mp 163-165 ˚C; IR (KBr): 3448, 2984, 1772, 1619, 1533, 1459, 1420, 1368, 1319, 1259, 1224, 1154, 1099, 1077, 1027, 980, 914, 852, 815
cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.44 (s, 1 H), 7.29-7.23 (m, 3 H), 6.93-6.92 (d, J = 6.8 Hz, 2 H), 4.93 (d, J = 16.0 Hz, 1 H), 4.87 (d, J = 16.0 Hz, 1 H), 4.85-4.53 (m, 4 H), 4.37-4.25 (m, 6 H), 2.90 (s, 2 H), 2.33 (s, 3 H), 2.20 (s, 3 H), 1.37-1.29 (m, 6 H); ^¹³C NMR (CDCl₃, 150 MHz): δ = 165.6, 165.4, 156.9, 156.4, 152.1, 138.5, 136.3, 135.0, 133.2, 129.1, 128.1, 127.4, 126.3, 79.7, 76.0, 63.4, 63.2, 59.9, 59.8, 53.9, 45.2, 39.7, 19.9, 14.5, 13.9, 13.8; HRMS: m/z [M + H]⁺ calcd for C₂₉H₃₂N₆O₈: 592.2282; found: 593.2354.
Compound 7f: Yield: 52%; white solid; mp 158-160 ˚C; IR (KBr): 3062, 2977, 2937, 2847, 1754, 1718, 1520, 1470, 1423, 1276, 814, 744 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz):
δ = 7.86 (d, J = 9.2 Hz, 1 H), 7.28-7.22 (m, 3 H), 6.93-6.89 (m, 3 H), 5.80 (d, J = 16.8 Hz, 1 H), 5.74 (d, J = 16.0 Hz, 1 H), 4.68 (d, J = 14.0 Hz, 1 H), 4.62 (d, J = 16.8 Hz, 1 H), 4.52 (d, J = 14.4 Hz, 1 H), 4.40 (d, J = 14.0 Hz, 1 H), 4.38-4.21 (m, 6 H), 4.00 (s, 3 H), 2.99 (d, J = 13.2 Hz, 1 H), 2.66 (d, J = 13.6 Hz, 1 H), 1.38-1.25 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.7, 165.5, 160.3, 156.7, 144.2, 136.2, 133.5, 129.1, 128.1, 127.5, 126.9, 126.0, 110.6, 79.3, 63.4, 63.2, 60.6, 58.9, 56.8, 53.9, 38.6, 36.7, 13.9, 13.8; HRMS: m/z [M + H]⁺ calcd for C₂₈H₃₀N₆O₉: 594.2074; found: 595.2147.
Compound 7g: Yield: 56%; white solid; mp 233-234 ˚C; IR (KBr): 3448, 2979, 2935, 2825, 1950, 1754, 1721, 1585, 1558, 1497, 1465, 1417, 1372, 1301, 1277, 1252, 1213, 1168, 1141, 1110, 1073, 1029, 986, 961, 910, 862, 828
cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.83 (d, J = 8.0 Hz, 1 H), 7.47 (d, J = 8.0 Hz, 1 H), 6.94-6.88 (m, 3 H), 5.45 (d, J = 16.0 Hz, 1 H), 4.88 (d, J = 16.0 Hz, 1 H), 4.68-4.39 (m, 4 H), 4.37-4.26 (m, 6 H), 2.94 (d, J = 14.0 Hz, 1 H), 2.88 (d, J = 14.0 Hz, 1 H), 1.38-1.30 (m, 6 H); ^¹³C NMR (CDCl₃, 150 MHz): δ = 165.7, 165.5, 156.9, 156.7, 139.9, 139.4, 136.8, 136.3, 130.8, 129.3, 129.0, 128.0, 127.3, 100.6, 79.4, 76.2, 63.2, 63.1, 60.0, 59.6, 53.8, 49.7, 46.0, 13.4, 13.8; HRMS: m/z [M + H]⁺ calcd for C₂₇H₂₈IN₅O₆: 645.1084; found: 646.1157.
Compound 7h: Yield: 82%; white solid; mp 212-213 ˚C; IR (KBr): 3448, 3066, 2960, 2930, 2851, 2153, 1772, 1652, 1587, 1544, 1461, 1419, 1368, 1318, 1254, 1223, 1157, 1098, 1098, 1077, 1027, 987, 919, 905, 859 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.44 (d, J = 7.6 Hz, 2 H), 7.29-7.20 (m, 4 H), 6.93 (d, J = 7.6 Hz, 2 H), 5.73 (d, J = 16.0 Hz, 1 H), 4.84 (d, J = 16.0 Hz, 1 H), 4.70 (d, J = 14.4 Hz, 1 H), 4.62 (d, J = 14.4 Hz, 1 H), 4.60 (d, J = 16.4 Hz, 1 H), 4.49 (d, J = 16.4 Hz, 1 H), 4.38-4.25 (m, 6 H), 3.02 (d, J = 13.2 Hz, 1 H), 2.87 (d, J = 13.2 Hz, 1 H), 1.38-1.26 (m, 6 H), 0.30 (s, 9 H); ^¹³C NMR (CDCl₃, 150 MHz): δ = 166.1, 165.8, 157.1, 156.6, 138.5, 136.6, 132.4, 130.3, 129.2, 128.9, 128.2, 128.0, 127.5, 127.3, 123.9, 102.3, 99.6, 80.1, 76.1, 63.3, 63.1, 60.4, 59.5, 54.0, 45.7, 42.5, 14.0, 13.9; HRMS: m/z [M + H]⁺ calcd for C₃₂H₃₇N₅O₆Si: 615.2513; found: 616.2586.
Compound 7i: Yield: 58%; white solid; mp 288-289 ˚C; IR (KBr): 3424, 3059, 2983, 2930, 2846, 1739, 1721, 1588, 1545, 1460, 1420, 1368, 1315, 1259, 1224, 1172, 1148, 1080, 1026, 984, 917, 905, 854, 802 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 8.63 (d, J = 8.4 Hz, 1 H), 7.90-7.84 (m, 2 H), 7.65-7.45 (m, 5 H), 7.33-7.29 (m, 2 H), 7.25-6.97 (m, 3 H), 6.95-5.90 (m, 2 H), 5.95 (d, J = 16.0 Hz, 1 H), 4.90 (d, J = 16.0 Hz, 1 H), 4.75-4.63 (m, 4 H), 4.57-4.26 (m, 6 H), 3.06 (d, J = 13.6 Hz, 1 H), 2.97 (d, J = 13.6 Hz, 1 H), 1.38-1.25 (m, 6 H); ^¹³C NMR (CDCl₃, 150 MHz): δ = 165.9, 165.6, 156.9, 156.6, 137.8, 136.8, 133.3, 133.1, 132.3, 130.9, 130.3, 129.3, 128.9, 127.8, 127.5, 126.9, 126.5, 126.4, 125.3, 124.2, 120.7, 92.3, 91.6, 80.1, 75.9, 63.4, 63.3, 59.4, 53.9, 45.7, 42.8, 13.9 cm^-¹. HRMS: m/z [M + H]⁺ calcd for C₃₉H₃₅N₅O₆: 669.2587; found: 670.2660.
Compound 7j: Yield: 25%; white solid; mp 177-179 ˚C; IR (KBr): 3066, 2956, 2922, 1737, 1716, 1460, 1416, 1266, 850, 750 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.51-7.45 (m, 4 H), 7.32-7.29 (m, 2 H), 6.94 (d, J = 2.0 Hz, 2 H), 4.86 (d, J = 15.6 Hz, 2 H), 4.64 (d, J = 15.6 Hz, 2 H), 4.60 (d, J = 14.0 Hz, 2 H), 4.39-4.28 (m, 6 H), 2.90 (s, 2 H), 1.38-1.25 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.8, 165.6, 157.0, 140.5, 136.2, 130.0, 129.1, 128.0, 125.0, 122.8, 80.3, 75.9, 63.3, 59.9, 53.2, 45.5, 29.7, 14.0; HRMS: m/z [M + H]⁺ calcd for C₂₈H₂₈F₃N₅O₆: 587.1992; found: 588.2064.
Compound 7k: Yield: 65%; white solid; mp136-139 ˚C; IR (KBr): 3053, 2992, 2966, 2906, 1761, 1715, 1416, 1415, 1254, 820, 739 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.49-7.46 (m, 2 H), 7.29-7.26 (m, 2 H), 7.01 (d, J = 7.6 Hz, 2 H), 6.75 (d, J = 8.0 Hz, 2 H), 4.86 (d, J = 16.0 Hz, 2 H), 4.64 (d, J = 16.0 Hz, 2 H), 4.37-4.27 (m, 6 H), 2.84 (s, 2 H), 2.27 (s, 3 H), 1.38-1.30 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 166.0, 165.7, 156.9, 136.8, 136.2, 133.4, 130.0, 128.9, 128.7, 128.0, 80.3, 76.0, 63.2, 63.1, 59.8, 53.5, 45.4, 21.0, 14.0, 13.9; HRMS: m/z [M + H]⁺ calcd for C₂₈H₃₁N₅O₆: 533.2274; found: 534.2347.
Compound 7l: Yield: 72%; white solid; mp 190-192 ˚C; IR (KBr): 3068, 2981, 2954, 2841, 1766, 1738, 1719, 1466, 1421, 1226, 736 cm^-¹; ^¹H NMR (CDCl₃, 400 MHz): δ = 7.47-7.43 (m, 2 H), 7.27-7.24 (m, 2 H), 6.12 (s, 2 H), 4.86 (d, J = 16.0 Hz, 2 H), 4.65 (d, J = 15.6 Hz, 4 H), 4.38-4.29 (m, 6 H), 3.81 (s, 6 H), 3.79 (s, 3 H), 2.81 (s, 2 H), 1.38-1.31 (m, 6 H); ^¹³C NMR (CDCl₃, 100 MHz): δ = 165.8, 165.5, 156.9, 152.5, 136.6, 136.2, 131.8, 129.7, 127.8, 105.7, 80.2, 75.8, 63.2, 63.1, 60.6, 59.6, 55.8, 54.0, 45.3, 13.9, 13.8; HRMS: m/z [M + H]⁺ calcd for C₃₀H₃₅N₅O₉: 609.2435; found: 610.2508.

19

Crystal data for compound 7a: C₂₇H₂₉N₅O₆; MW = 519.55; monoclinic; a = 15.655(4), b = 8.752(2), c = 19.427(5) Å, β = 110.550(5)˚; V = 2492.4(11) Å^³; T = 292(2) K; space group P2₁/n; Z = 4; µ(Mo-K_α) = 0.100 mm^-¹; 13703 reflections measured, 4889 unique (R _int = 0.0476) which were used in all calculations. The final wR2 (F ₂) was 0.1980 (all data).
For compound 7b: C₂₉H₃₃N₅O₆; MW = 547.60; monoclinic; a = 9.9597(9), b = 23.109(2), c = 12.4028(11) Å, β = 101.193(2)˚; V = 2800.3(4) Å^³; T = 292(2) K; space group P2₁/c; Z = 4; µ(Mo-K_α) = 0.092 mm^-¹; 14003 reflections measured, 4926 unique (R _int = 0.0343) which were used in all calculations. The final wR2 (F ₂) was 0.1755 (all data).
For compound 7c: C₂₉H₃₃N₅O₈; MW = 579.60; monoclinic; a = 8.1464(6), b = 23.9524(17), c = 15.0281(11) Å, β = 104.7310(10)˚; V = 2836.0(4) Å^³; T = 292(2) K; space group P2₁/n; Z = 4; µ(Mo-K_α) = 0.100 mm^-¹; 33110 reflections measured, 6772 unique (R _int = 0.0987) which were used in all calculations. The final wR2 (F ₂) was 0.1729 (all data).
For compound 7d: C₂₇H₂₇Br₂N₅O₆; MW = 677.36; triclinic; a = 9.136(3), b = 10.144(3), c = 15.028(4) Å, α = 90.784(5)˚, β = 94.628(5)˚, γ = 94.984(5)˚; V = 1382.6(7) Å^³; T = 292(2) K; space group P1, Z = 2; µ(Mo-K_α) = 2.983 mm^-¹; 13279 reflections measured, 5386 unique (R _int = 0.1158) which were used in all calculations. The final wR2 (F ₂) was 0.1795 (all data).
For compound 7e: C₂₉H₃₂N₆O₈; MW = 592.61; monoclinic; a = 7.9571(4), b = 15.6173(6), c = 22.8959(10) Å, β = 94.0820(10)˚; V = 2838.0(2) Å^³; T = 292(2) K; space group P2₁/c; Z = 4; µ(Mo-K_α) = 0.103 mm^-¹; 21931 reflections measured, 4992 unique (R _int = 0.0254) which were used in all calculations. The final wR2 (F ₂) was 0.1761 (all data).
For compound 7f: C₅₆H₆₄N₁₂O₁₉; MW = 1209.19; tetragonal; a = 15.9660(6), b = 15.9660(6), c = 11.1270(9) Å, α = β = γ = 90.00˚; V = 2836.4(3) Å^³; T = 292(2) K; space group P4₃; Z = 2; µ(Mo-K_α) = 0.108 mm^-¹; 32120 reflections measured, 6183 unique (R _int = 0.1055) which were used in all calculations. The final wR2 (F ₂) was 0.1147 (all data).
For compound 7g: C₂₇H₂₈IN₅O₆; MW = 645.44; monoclinic; a = 9.0743(10), b = 25.339(3), c = 11.6956(13) Å, β = 90.212(2)˚; V = 2689.2(5) Å^³; T = 292(2) K; space group P2₁/c; Z = 4; µ(Mo-K_α) = 1.242 mm^-¹; 30097 reflections measured, 5852 unique (R _int = 0.0924) which were used in all calculations. The final wR2 (F ₂) was 0.1632 (all data).
For compound 7j: C₂₈H₂₈F₃N₅O₆; MW = 587.55; triclinic; a = 9.2056(13), b = 12.8972(18), c = 13.3762(19) Å, α = 113.437(2)˚, β = 98.874(2)˚, γ = 99.525(2)˚; V = 1393.8(3) Å^³; T = 292(2) K; space group P1; Z = 2; µ(Mo-K_α) = 0.113 mm^-¹; 14646 reflections measured, 5445 unique (R _int = 0.0559) which were used in all calculations. The final wR2 (F ₂) was 0.1554 (all data).
For compound 7k: C₂₈H₃₁N₅O₆; MW = 533.58; orthorhombic; a = 18.049(4), b = 18.263(4), c = 8.0492(17) Å, α = β = γ = 90.00˚; V = 2653.3(10) Å^³; T = 292(2) K; space group Pna2₁; Z = 4; µ(Mo-K_α) = 0.096 mm^-¹; 26452 reflections measured, 3099 unique (R _int = 0.0885) which were used in all calculations. The final wR2 (F ₂) was 0.1101 (all data).
For compound 7l: C₃₀H₃₅N₅O₉; MW = 613.63; monoclinic; a = 8.9216(5), b = 29.5203(17), c = 11.5079(6) Å, β = 90.5000(10)˚; V = 3030.7(3) Å^³; T = 292(2) K; space group P2₁/n; Z = 4; µ(Mo-K_α) = 0.101 mm^-¹; 23651 reflections measured, 5919 unique (R _int = 0.0768) which were used in all calculations. The final wR2 (F ₂) was 0.2164 (all data).
CCDC-724320 (7a); CCDC-724321 (7b); CCDC-724322 (7c); CCDC-724323 (7d); CCDC-724324 (7e); CCDC-724325 (7f); CCDC-724326 (7g); CCDC-724327 (7j); CCDC-724328 (7k); CCDC-724329 (7l). These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; email: deposit@ccdc.cam.ac.uk].

Supplementary Material

Supporting Information