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within the macrocycle (Figure 7). (Release 8.0) software using PM3, AMBER and MM+ methods and no influence of solvents was taken into account in the calculations. 33,34 Circular Dichroism (CD) measurements were carried out using Jasco-J-810 Spectropolarimeter in H 2O and DMSO. (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbohydrazide 2: To a stirred solution of (4R,5R)-dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 1 (4.76 g, 21.83 mmol) in absolute ethanol (20 mL) was added hydrazine monohydrate (2.3 mL, 72.76 mmol) and the mixture was refluxed for 12 h. The solvent was evaporated under vacuum and the resulting oil was patitionated between ethyl acetate and water (10 mL). To the water phase was added ethanol (200 mL) and anhydrous Na 2SO 4. The solvent was filtered off and evaporated under vacuum to afford the title product as a white gummy material (4.21 g, 88%). 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.3 (brs, 2H; NH), 4.4 (brs, 2H; CH), 4.2 (brs, 4H; NH 2), 1.3 ppm (s, 6H; CH 3); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =167.8, 112.2, 77.2, 26.6 ppm; FT-IR: ṽ = 3316 (NH and NH 2), 1660 cm –1 (C[dbond]O); HRMS (ESI-): m/z calcd. for [C 7H 14N 4O 4+ Na + ]: 241.0907 [M+ Na + ]; found: 241.0900. Figure 7. Circular Dichroism spectra for the novel macrocycles and their precursors. Conclusion In summary, we have developed a versatile methodology for the synthesis of a novel class of chiral non-racemic tetra-carbohydrazide cyclophane macrocycles. Both (R) and (S) enantiomers can be readily synthesised in short reaction steps, high purity and quantitative yields. The novel macrocycles can be functionalized by simple choice of the target ketone or diketal to be protected. This can lead to the synthesis of supramolecular architectures with fascinating structures and improved solubility. In addition, the dicarbohydrazide precursors showed interesting molecular selfassembly in the gas phase to form hydrogen bonded macrocycles, which has been confirmed by ESI-TOF MS. Further studies aimed at assessing the molecular recognition properties of the novel macrocycles are under investigation. Experimental Section All the reagents used for the reactions were purchased from Sigma-Aldrich, Applichem or Flucka (Germany) and were used as obtained. Whenever possible the reactions were monitored by thin layer chromatography (TLC). TLC was performed on Macherey- Nagel aluminium-backed plates pre-coated with silica gel 60 (UV 254). Melting points were determined in open capillaries using a Buechl B-545 melting point apparatus and are not corrected. Infrared spectra were determined using a Vector-33 Bruker FT-IR spectrometer. The samples were measured directly as solids or oils; ṽ max values were expressed in cm –1 and were given for the main absorption bands. 1 H-NMR and 13 C- NMR spectra were acquired on a JEOL ECX-400 spectrometer operating at 400 MHz for 1 H-NMR and 100 MHz for 13 C-NMR in [D6]DMSO or [D7]DMF using a 5 mm probe. The chemical shifts (δ) are reported in parts per million and were referenced to the residual solvent peak. The following abbreviations are used: s, singlet; m, multiplet; br, broad signal. Mass spectra were recorded using Bruker HCTultra and high resolution Bruker Daltonics micrOTOF instruments from DMSO, DMF and acetonitrile or water using the positive electrospray ionisation ESI- and APCI-MS modes. Calibration was carried out using a 0.1 M solution of sodium formate in the enhanced quadratic mode prior to each experimental run. The results of measurements were processed using Compass 1.3 data analysis software for a Bruker Daltonics time-of-flight mass spectrometer (micrOTOF). Molecular modeling was carried out with HyperChem (4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbohydrazide 4: To a stirred solution of (4S,5S)-dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 3 (5.8 g, 26.60 mmol) in absolute ethanol (20 mL) was added hydrazine monohydrate (2.8 mL, 88.68 mmol) and the mixture was refluxed for 12 h. The solvent was evaporated under vacuum and the resulting oil was partionated between ethyl acetate and water (10 mL). To the water phase was added ethanol (200 mL) and anhydrous Na 2SO 4. The solvent was filtered off and evaporated under vacuum to afford the title product as a white gummy material (4.50 g, 77%). 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.3 (brs, 2H; NH), 4.4 (brs, 2H; CH), 4.3 (brs, 4H; NH 2), 1.3 ppm (s, 6H; CH 3); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =167.8, 112.2, 77.2, 26.6 ppm; FT-IR: ṽ = 3316 (NH and NH 2), 1660 cm –1 (C[dbond]O); HRMS (ESI-): m/z calcd. for [C 7H 14N 4O 4+Na + ]: 241.0907 [M+ Na + ]; found: 241.0900. (2R,3R)-1,4-dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 7: To a stirred solution of (+)-diethyl L-tartrate (7.5 mL, 44 mmol) in toluene (150 mL) were added 1,1- dimethoxycyclohexane (10 mL, 65.8 mmol) and PTSA (103 mg, 0.54 mmol). The flask was fitted with a Soxhlet extractor, reflux condenser and a thimble containing freshly activated 4 Å molecular sieves (15 g). The mixture was refluxed for 7h, during which the thimble was recharged with fresh molecular sieves twice. The reaction mixture was neutralised with anhydrous sodium bicarbonate and the suspension was filtered off. The solvent was evaporated under vacuum and the residue was partionated between ethyl acetate and water, washed with saturated sodium bicarbonate (70 mL), brine (70 mL) and dried with Na 2SO 4. The solvent was filtered off and evaporated under vacuum. The crude oil (11.17 g) was dissolved without further purification in absolute ethanol (50 mL) and hydrazine monohydrate was added (4.4 mL, 140 mmol). The mixture was refluxed for 7 h and the solvent was evaporated under vacuum. The residue was dissolved in water (10 mL) and extracted with ethyl acetate (3×50 mL). The water extract was dissolved in ethanol (200 mL), dried with Na 2SO 4 and evaporated under vacuum to afford the title product as pale yellow gummy material (5.58 g, 55%). 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.2 (brs, 2H; NH), 4.4 (brs, 2H; CH), 4.3 (brs, 4H; NH 2), 1.4-1.5 (m, 8H; CH 2), 1.2 ppm (m, 2H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =167.9, 112.9, 76.9, 35.7, 24.9, 23.8 ppm; FT-IR: ṽ = 3313 (NH and NH 2), 1666 cm –1 (C[dbond]O); HRMS (ESI-): m/z calcd. for [C 10H 18N 4O 4+Na + ]: 281.1220 [M+ Na + ]; found: 281.1231. (2S,3S)-1,4-dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 9: To a stirred solution of (-)-diethyl D-tartrate (7.5 mL, 44 mmol) in toluene (150 mL) were added 1,1- dimethoxycyclohexane (10 mL, 65.8 mmol) and PTSA (103 mg, 0.54 mmol). The flask was fitted with a Soxhlet extractor, reflux condenser and a thimble containing freshly activated 4 Å molecular sieves (15 g). The mixture was refluxed for 7h, during which 5
the thimble was recharged with fresh molecular sieves twice. The reaction mixture was neutralised with anhydrous sodium hydrogen carbonate and the suspension was filtered off. The solvent was evaporated under vacuum and the residue was partionated between ethyl acetate and water, washed with saturated sodium bicarbonate (70 mL), brine (70 mL) and dried with Na 2SO 4. The solvent was filtered off and evaporated under vacuum. The crude oil (11.42 g) was dissolved without further purification in absolute ethanol (50 mL) and hydrazine monohydrate was added (6.3 mL, 201 mmol). The mixture was refluxed for 7 h and the solvent was evaporated under vacuum. The residue was dissolved in water (10 mL) and extracted with ethylacetate (3×50 mL). The water extract was dissolved in ethanol (200 mL), dried with Na 2SO 4 and evaporated under vacuum to afford the title product as pale yellow gummy material (5.97 g, 56%). 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.3 (brs, 2H; NH), 4.4 (brs, 2H; CH), 4.0 (brs, 4H; NH 2), 1.4-1.6 (m, 8H; CH 2), 1.2-1.3 ppm (m, 2H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =167.8, 112.8, 76.9, 35.8, 25.0, 23.8 ppm; FT-IR: ṽ = 3316 (NH and NH 2), 1666 cm –1 (C[dbond]O); HRMS (ESI-): m/z calcd. for [2 (C 10H 18N 4O 4)+Na + ]: 539.2545 [2M+ Na + ]; found: 539.2550. General procedures for the synthesis of tetra-carbohydrazide cyclophanes 10-17: To a stirred solution of dicarbohydrazide 2, 4, 7 or 9 (1.2 mmol) and the corresponding dialdehyde (1 mmol) in MeOH (< 0.05 M) was added two drops of AcOH. The reaction mixture was refluxed for 7 h. The precipitate was filtered off, washed with water, chloroform and dried to give the corresponding macrocycle in a quantitative yield. (3S,4S,16S,17S)-Tetra-carbohydrazide cyclophane 13: Prepared from (4S,5S)- dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 4 and 4,4ʹ-diformyltriphenylamine as a yellow precipitate (99%). M.p. > 325 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.5 (brs, 4H; NH), 8.2 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.8 (brs, 1H; CH=N), 7.5 (brs, 1H; CH=N), 7.2-7.4 (m, 8H; ArH), 7.0-7.2 (m, 8H; ArH), 6.5-6.8 (m, 10H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.3-1.4 ppm (m, 12H; CH 3); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ = 170.6, 165.3, 148.7, 146.3, 144.4, 130.4, 129.1, 126.1, 123.5, 112.9, 77.5, 26.6 ppm; FT-IR: ṽ = 3212 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 54H 50N 10O 8+Na + ]: 989.3933 [M+ Na + ]; found: 989.3752. (3R,4R,16R,17R)-Tetra-carbohydrazide cyclophane 14: Prepared from (2R,3R)-1,4- dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 7 and 4-(4-formylphenoxy)-benzaldehyde as a white precipitate (98%). M.p. > 320 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.6 (m, 4H; NH), 8.3 (brs, 1H; CH=N), 8.0 (brs, 1H; CH=N), 7.8 (brs, 1H; CH=N), 7.4-7.7 (m, 9H; CH=N and ArH), 6.6-7.0 (m, 8H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.6 (brs, 8H; CH 2), 1.5 (brs, 8H; CH 2), 1.3 (brs, 4H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.8, 165.7, 158.2, 148.5, 144.2, 129.9, 119.4, 113.5, 77.2, 35.8, 25.0, 23.8 ppm; FT-IR: ṽ = 3206 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 48H 48N 8O 10+ H + ]: 897.3566 [M+ H + ]; found: 897.3526. (3R,4R,16R,17R)-Tetra-carbohydrazide cyclophane 10: Prepared from (4R,5R)- dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 2 and 4-(4-formylphenoxy)-benzaldehyde as a white precipitate (97%). M.p. > 310 °C. 1 H NMR (400 MHz, [D6] DMSO, 25 °C, TMS): δ = 11.5-11.6 (m, 4H; NH), 8.3 (brs, 1H; CH=N), 8.0 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.5-7.7 (m, 9H; CH=N and ArH), 6.6-7.0 (m, 8H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.40-1.45 ppm (m, 12H; CH 3); 1 H NMR (400 MHz, [D7]DMF, 25 °C, TMS): δ = 11.6 (brs, 2H; NH), 11.5 (brs, 2H; NH), 8.5 (brs, 1H; CH=N), 8.2 (brs, 1H; CH=N), 8.1 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.5-7.8 (m, 8H; ArH), 6.8-7.1 (m, 8H; ArH), 5.6 (brs, 2H; CH), 4.9 (brs, 1H; CH), 4.8 (brs, 1H; CH), 1.4-1.5 ppm (m, 12H; CH 3); 13 C NMR (100 MHz, [D7]DMF, 25 °C, TMS): δ =170.5, 165.8, 158.4, 148.4, 144.2, 129.5, 119.2, 113.0, 77.8, 25.9 ppm; FT-IR: ṽ = 3208 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 42H 40N 8O 10+Na+]: 839.2760 [M+ Na + ]; found: 839.2795. (3R,4R,16R,17R)-Tetra-carbohydrazide cyclophane 11: Prepared from (4R,5R)- dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 2 and 4,4ʹ-diformyltriphenylamine as a yellow precipitate (99%). M.p. > 325 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.5 (brs, 4H; NH), 8.2 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.8 (brs, 1H; CH=N), 7.5 (brs, 1H; CH=N), 7.2-7.4 (m, 8H; ArH), 6.8-7.0 (m, 8H; ArH), 6.5-6.8 (m, 10H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.3-1.4 ppm (m, 12H; CH 3); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.6, 165.3, 148.7, 146.5,144.4, 130.4, 129.1, 126.2, 123.2, 112.8, 77.5, 26.6 ppm; FT-IR: ṽ = 3212 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 54H 50N 10O 8+Na + ]: 989.3705 [M+ Na + ]; found: 989.3668. (3S,4S,16S,17S)-Tetra-carbohydrazide cyclophane 12: Prepared from (4S,5S)- dimethyl-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate 4 and 4-(4-formylphenoxy)-benzaldehyde as a white precipitate (94%). M.p. > 300 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.6 (m, 4H; NH), 8.3 (brs, 1H; CH=N), 8.0 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.5-7.7 (m, 9H; CH=N and ArH), 6.6-7.0 (m, 8H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.3-1.4 ppm (m, 12H; CH 3); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.6, 165.5, 158.2, 148.5, 144.3, 129.7, 119.4, 112.9. 77.5, 26.6 ppm; FT-IR: ṽ = 3211 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 42H 40N 8O 10+Na + ]: 839.2760 [M+ Na + ]; found: 839.2744. (3R,4R,16R,17R)-Tetra-carbohydrazide cyclophane 15: Prepared from (2R,3R)-1,4- dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 7 and 4,4ʹ-diformyltriphenylamine as a yellow precipitate (99%). M.p. > 310 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.5 (m, 4H; NH), 8.2 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.8 (brs, 1H; CH=N), 7.5 (brs, 1H; CH=N), 7.2-7.4 (m, 8H; ArH), 7.0-7.1 (m, 8H; ArH), 6.5-6.7 (m, 10H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.6 (brs, 8H; CH 2), 1.5 (brs, 8H; CH 2), 1.3 (brs, 4H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.9, 165.5, 146.3, 144.3, 130.4, 129.1, 126.2, 123.5, 113.4, 77.2, 35.9, 25.0, 24.0 ppm; FT-IR: ṽ = 3218 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 60H 58N 10O 8+H + ]: 1047.4512 [M+ H + ]; found: 1047.4521. (3S,4S,16S,17S)-Tetra-carbohydrazide cyclophane 16: Prepared from (2S,3S)-1,4- dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 9 and 4-(4-formylphenoxy)-benzaldehyde as a white precipitate (88%). M.p. > 310 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.6 (m, 4H; NH), 8.3 (brs, 1H; CH=N), 8.0 (brs, 1H; CH=N), 7.8 (brs, 2H; CH=N), 7.4-7.7 (m, 8H; ArH), 6.6-7.0 (m, 8H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.6 (brs, 8H; CH 2), 1.5 (brs, 8H; CH 2), 1.3 (brs, 4H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.8, 165.6, 158.2, 148.5, 144.2, 129.7, 119.4, 113.5, 77.2, 35.9, 25.0, 24.0 ppm FT-IR: ṽ = 3220 (NH and NH 2), 1682 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 48H 48N 8O 10+H + ]: 897.3566 [M+ H + ]; found: 897.3539. (3S,4S,16S,17S)-Tetra-carbohydrazide cyclophane 17: Prepared from (2S,3S)-1,4- dioxaspiro-[4.5]-decane-2,3-dicarbohydrazide 9 and 4,4ʹ-diformyltriphenylamine as a yellow precipitate (89%). M.p. > 310 °C. 1 H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 11.5 (m, 4H; NH), 8.2 (brs, 1H; CH=N), 7.9 (brs, 1H; CH=N), 7.8 (brs, 1H; CH=N), 7.5 (brs, 1H; CH=N), 7.2-7.4 (m, 8H; ArH), 6.9-7.1 (m, 8H; ArH), 6.5-6.9 (m, 10H; ArH), 5.4 (brs, 2H; CH), 4.7 (brs, 1H; CH), 4.5 (brs, 1H; CH), 1.6 (brs, 8H; CH 2), 1.5 (brs, 8H; CH 2), 1.3 (brs, 4H; CH 2); 13 C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ =170.9, 165.4, 146.5, 144.2, 130.4, 128.8, 126.0, 123.4, 113.4, 77.2, 35.8, 25.0, 24.0 ppm; FT-IR: ṽ = 3210 (NH and NH 2), 1681 cm –1 (C[dbond]O and C[dbond]N); HRMS (APCI-): m/z calcd. for [C 60H 58N 10O 8+H + ]: 1047.4512 [M+ H + ]; found: 1047.4509. Acknowledgment Hany Nour deeply thanks the financial support from Deutscher 6
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The Development of Novel Antibiotic
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Declaration of Authorship I, Hany N
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Abstract Over the past few decades,
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Chapter 2 Trianglimine Chemistry
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Figure 2.4 Trianglimines 10-12 with
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Abbreviations ACN AcOH Ala Acetonit
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RMS ROESY SjGST TFA THF TLC TMS TOC
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Introduction complete remodel of th
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Introduction following protonation.
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Introduction Lehn and co-workers re
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Introduction Figure 1.8 Generation
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Introduction Figure 1.11 Synthetic
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Introduction Figure 1.13 Generation
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Introduction 1.3.11 Boronic ester e
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Introduction References 1. E. Mouli
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Introduction 51. B. Shi, M. F. Grea
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Introduction Figure 2.2 shows compu
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Introduction incorporate β-cyclode
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Introduction Trianglamine-Zn(R) 2 c
Page 39 and 40: Introduction 24. J. Gajewy, J. Gawr
Page 41 and 42: Scope of Work Scope of Work In this
Page 43 and 44: Scope of Work can be obtained from
Page 45 and 46: Scope of Work Figure 3.4 Structures
Page 47 and 48: Scope of Work References 1. G. Wrig
Page 49 and 50: Organic & Biomolecular Chemistry Ci
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Page 63 and 64: Paper 2 Rapid Commun. Mass Spectrom
Page 65 and 66: Trianglimine formation mechanism by
Page 75 and 76: Paper 3 Org. Biomol. Chem., 2012, 1
Page 81 and 82: View Online Table 2 Distances (Å)
Page 85 and 86: Paper 4 Chem. Eur. J., 2012, submit
Page 87 and 88: (4R,5R)- and (4S,5S)-dimethyl-2,2-d
Page 89: that two distinct conformational is
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Page 95 and 96: INTRODUCTION No single class of dru
Page 97 and 98: EXPERIMENTAL All the solvents and r
Page 99 and 100: (b) Refluxing macrocycles 5, 6 and
Page 101 and 102: Scheme 1. Graphical representation
Page 103 and 104: Figure 1. A plot of relative intens
Page 105 and 106: In contrast, formation of library m
Page 107 and 108: Figure 5. Generated dynamic library
Page 109 and 110: macrocycle 32 from the dynamic libr
Page 111 and 112: The polar carbamate group participa
Page 113 and 114: [2] WHO World health report 2003. h
Page 115 and 116: [32] B. Lienard, N. Selevsek, N. Ol
Page 117 and 118: FULL PAPER Synthesis and ESI-MS Com
Page 119 and 120: ability of the technique to provide
Page 121 and 122: aimed at assessing molecular recogn
Page 123 and 124: Paper 7 manuscript Synthesis, self-
Page 125 and 126: 2 Similar to the case of trianglimi
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Page 129 and 130: 6 The newly synthesized receptors s
Page 131 and 132: 8 27. Nour, H. F.; Hourani, N.; Kuh
Page 133 and 134: 120| P a g e Appendix
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Supplementary Material (ESI) for Or
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Monitoring the [3+3]-cyclocondensat
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Monitoring the cyclocondensation re
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Product ions appeared as [M+H] + Fi
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Scheme 1. Assigned higher oligomers
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Supplementary Information: Synthesi
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Scheme 4. Proposed fragmentation me
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DMSO Figure 1. 1 H-NMR spectrum for
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Figure 6. 13 C-NMR spectrum for (4S
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Intens. 7 x10 1.5 200.7 1.0 0.5 0.0
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Intens. 7 x10 200.7 1.5 1.0 0.5 0.0
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Intens. 4 x10 577.2 2.0 1.5 1.0 451
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HN N O O R R NH O O N N HN R O O O
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Intens. 5 x10 727.2 2.0 1.5 1.0 O O
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Intens. 5 x10 697.1 1.5 1.0 728.2 0
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O O O O HN N O O NH N HN N O O NH N
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Figure 38. 1 H-NMR spectrum for mac
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Intens. 5000 276.8 4000 3000 2000 1
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Intens. 7 x10 599.1 1.5 1.0 0.5 0.0
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(a) HN N O O NH O O N (b) HN N O NH
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Scheme 11. Proposed fragmentation m
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Scheme 14. Proposed fragmentation m
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Intens. 4 x10 550.9 3 2 1 0 500 100
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Figure 68. 2D-ROESY spectrum for ma
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Supplementary Information: Novel sy
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Intens. 6 x10 0.8 0.6 0.4 240.9 459
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Figure 9. 1 H-NMR spectrum for macr
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Intens. 5 x10 1.5 968.1 1.0 0.5 813
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Intens. 5 x10 897.4 4 2 335.3 707.3
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Scheme 3. Suggested fragmentation m
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Molecular modelling data for the co
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Figure 1. 1 H NMR spectrum for dica
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Intens. 2000 1493.6091 Host-Guest 1
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Intens. [%] 100 775.3 80 388.1 60 4
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Intens. 600 N HN O O 467.1916 400 O
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Intens. 6000 5000 HN N O O O O NH N
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Table 1. High resolution ESI-TOF da
Page 231 and 232:
i Figure 1. 1 H NMR spectrum for ma
Page 233 and 234:
i Figure 5. 1 H NMR spectrum for ma
Page 235 and 236:
i j Figure 9. 1 H NMR spectrum for
Page 237 and 238:
i Figure 13. DEPT-135 spectrum for
Page 239 and 240:
Scheme 1. General mechanism of frag
Page 241 and 242:
Intens. [%] 100 80 60 40 20 0 O H N
Page 243 and 244:
Intens. [%] 100 1131.3 80 60 40 20
Page 245 and 246:
Intens. 1500 1528.6088 1000 500 150
Page 247 and 248:
Intens. [%] 100 80 60 40 Free guest
Page 249 and 250:
Intens. 4 x10 1085.3575 1.25 1.00 0
Page 251 and 252:
Intens. [%] 100 80 Free guest 586.1
Page 253 and 254:
Synthesis, self-assembly and ESI-MS
Page 255 and 256:
O O HN NH HN O O NH HN O 11 O NH O
Page 257 and 258:
O O HN NH HN O O NH HN O 9 O NH O O
Page 259 and 260:
H 2 O DMSO DMSO Figure 6. 1 H-NMR a
Page 261 and 262:
Intens. 5 x10 5 -MS 487.1588 4 3 2
Page 263 and 264:
Intens. -MS 6 x10 0.8 0.6 0.4 0.2 1
Page 265 and 266:
Intens. -MS 6 x10 O O 350.9 1.5 1.0
Page 267 and 268:
Intens. [%] 100 -MS 486.9 Exact str
Page 269 and 270:
Intens. [%] -MS 100 486.9 80 60 975
Page 271 and 272:
Intens. [%] +MS 100 80 517.2 Exact
Page 273 and 274:
Intens. [%] 100 80 60 +MS 388.1 775
Page 275 and 276:
Intens. [%] 100 +MS 517.2 Exact str
Page 277 and 278:
Intens. [%] 100 80 +MS 1031.4939 7
Page 279 and 280:
Intens. [%] 100 +MS 517.2 Exact str
Page 281 and 282:
Intens. [%] 100 -MS 2 586.1 80 60 4
Page 283 and 284:
Intens. [%] 100 -MS 2 875.2 Exact s
Page 285 and 286:
Table 1. High resolution ESI-TOF/MS
Page 287 and 288:
274 | P a g e
Page 289 and 290:
276 | P a g e
Page 291:
4. H. Nour, A. López-Periago, N. K
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