*3.3. Chemical Syntheses*

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-dihydroxy-26**,**28-bis[2-(2-methoxyethoxy)ethoxy] calix[4]arene 1.** Under Ar, *tert*-butylcalix[4]arene (2 g, 3.08 mmol) was dissolved in anhydrous acetonitrile (40 mL) and 2-(2-methoxyethoxy)ethyl tosylate (1.86 g, 6.78 mmol) and K2CO<sup>3</sup> (1.06 g, 7.7 mmol) added. The reaction mixture was stirred at 72 ◦C for 4 d. After cooling, the solvent was changed to chloroform (40 mL), the insoluble ingredients were removed by filtration and the organic phase was washed with 10% aqueous HCl (2 × 30 mL) and water (2 × 30 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using column chromatography (petroleum ether:acetone = 10:1 → 5:1) to obtain **1** as colorless oil, which tends to crystallize after standing (2.31 g, 88%); mp 100 ◦C; R*<sup>f</sup>* 0.46 (petroleum ether:acetone = 2:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.95 (s, 18 H, <sup>t</sup>Bu), 1.30 (s, 18 H, <sup>t</sup>Bu), 3.30 (d, <sup>2</sup> *J* = 13.1 Hz, 4 H, CH2Ar), 3.39 (s, 6 H, OCH3), 3.61–3.64 (m, 4 H, OCH2), 3.83–3.86 (m, 4 H, OCH2), 3.96–4.00 (m, 4 H, OCH2), 4.16–4.19 (m, 4 H), 4.36 (d, <sup>2</sup> *J* = 13.1 Hz, CH2Ar), 6.77 (s, 4 H, ArH), 7.06 (s, 4 H, ArH), 7.15 (s, 2 H, OH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 31.2 (tBu), 31.9 (tBu), 33.9 (Cq), 34.0 (Cq), 59.2 (OCH3), 70.1 (OCH2), 71.1 (OCH2), 72.3 (OCH2), 75.4 (OCH2), 125.1, 125.6 (2 × CHAr), 128.0 (C Ar), 132.7, 141.4, 146.9, 150.0, 150.8 (6 <sup>×</sup> <sup>C</sup>Ar) ppm; MS (ESI+) *<sup>m</sup>*/*<sup>z</sup>* = 871 (M<sup>+</sup> + NH4), 876 (M<sup>+</sup> + Na), 892 (M<sup>+</sup> + K).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]calix[4]arene 2.** Under Ar, compound **1** (1 g, 1.17 mmol) was dissolved in anhydrous THF (40 mL) and NaH (234 mg, 5.86 mmol, 60% in mineral oil) added and stirred at rt for 30 min. Afterwards, a solution of ethyl bromoacetate (978 mg, 5.86 mmol) in 5 mL of THF was added and the resulting mixture stirred at 50 ◦C for 2 d. After cooling to rt, the solvent was changed to chloroform (40 mL), the insoluble ingredients were removed by filtration and the organic phase was washed with 10% aqueous HCl (3 × 30 mL) and water (2 × 30 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using column chromatography (petroleum ether:acetone = 4:1) to obtain **2** as lightyellow oil (1.07 g, 89%); R*<sup>f</sup>* 0.52 (petroleum ether:acetone = 2:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.03 (s, 18 H, <sup>t</sup>Bu), 1.12 (s, 18 H, <sup>t</sup>Bu), 1.29 (t, <sup>3</sup> *J* = 7.1 Hz, 6 H, CH3), 3.15 (d, <sup>2</sup> *J* = 12.9 Hz, 4 H, CH2Ar), 3.37 (s, 6 H, OCH3), 3.53–3.57 (m, 4 H, OCH2), 3.66–3.69 (m, 4 H, OCH2), 3.94 (t, <sup>3</sup> *J* = 5.6 Hz, 4 H, OCH2), 4.12 (t, <sup>3</sup> *J* = 5.6 Hz, 4 H, OCH2), 4.22 (q, <sup>3</sup> *J* = 7.2 Hz, 4 H, OCH2), 4.67 (d, <sup>2</sup> *J* = 12.9 Hz, 4 H, CH2Ar), 4.77 (s, 4 H, CH2C=O), 6.70 (s, 4 H, ArH), 6.83 (s, 4 H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): <sup>δ</sup> 14.4, 31.5, 31.6 (3 <sup>×</sup> CH3), 31.7 (CH2Ar), 33.9 (Cq), 34.0 (Cq), 59.2 (OCH3), 60.5 (OCH2), 70.4 (OCH2), 70.7 (OCH2), 71.3 (CH2C=O), 72.2 (OCH2), 73.2 (OCH2), 125.1 (CHAr), 125.5 (CHAr), 133.5, 134.0, 144.8, 145.2, 153.2, 153.4 (6 × CAr), 170.8 (C=O) ppm; MS (ESI+) *m*/*z* = 1042 (M<sup>+</sup> + NH4), 1047 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(carboxymethoxy)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]calix[4]arene 3.** Compound **2** (213 mg, 0.21 mmol) was dissolved in THF (20 mL), a solution of Me4NOH · 5 H2O (264 mg, 1.46 mmol) in methanol (1 mL) was added and the reaction mixture was stirred at 55 ◦C overnight. The major part of the solvent was removed and the product was precipitated with ice-cold aqueous HCl (6 M). The solid residue was filtered and washed with water (20 mL) and dissolved in chloroform (20 mL). The organic phase was washed with brine (3 × 10 mL) and 10% aqueous HCl (2 × 10 mL). After separation, the organic phase was dried over Na2SO4, the solvent was removed and the product was obtained as pale-orange solid (200 mg, >99%); mp 104–106 ◦C; <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.83 (s, 18 H, <sup>t</sup>Bu), 1.34 (s, 18 H, <sup>t</sup>Bu) 3.24 (d, <sup>2</sup> *J* = 13 Hz, 4 H, CH2Ar), 3.38 (s, 6H, OCH3), 3.23–3.26 (m, 4 H, OCH2), 3.73–3.75 (m, 4H, OCH2), 3.83–3.85 (m, 4 H, OCH2), 3.99–4.01 (m, 4 H, OCH2), 4.45 (d, <sup>2</sup> *J* = 13.0 Hz, 4 H, CH2Ar), 4.75 (s, 4 H, CH2C=O), 6.56 (s, 4 H, ArH), 7.17 (s, 4 H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 31.09 (CH2Ar), 31.14 (CH3), 31.8 (CH3), 33.9 (Cq), 34.4 (Cq), 59.2 (OCH3), 69.8 (OCH2), 70.5 (OCH2), 72.2 (OCH2), 72.3 (CH2C=O), 76.2 (OCH2), 125.5 (CHAr), 126.2 (CHAr), 132.3, 135.0, 146.1, 147.3, 150.2, 153.3 (6 <sup>×</sup> <sup>C</sup>Ar), 170.6 (C=O); MS (ESI−) *<sup>m</sup>*/*<sup>z</sup>* = 968 (M– <sup>−</sup> H).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]-25**,**27-bis(2-morpholino-2-oxoethyl)calix[4]arene 5.** Under Ar, compound **3** (100 mg, 0.103 mmol) was dissolved in CCl<sup>4</sup> (5 mL), oxalyl chloride (0.75 g, 5.88 mmol) dropwise added and the reaction mixture stirred at 65 ◦C for 5 h. After cooling to rt, the remaining oxalyl chloride and the solvent were removed under high vacuum and anhydrous DCM (5 mL) added. After cooling the solution to 0 ◦C, morpholine (22 mg, 0.26 mmol) and DIPEA (40 mg, 0.31 mmol) were added to resulting mixture was allowed to come to rt and was stirred at rt overnight. Afterwards, DCM (20 mL) was added and the organic phase washed with saturated hydrogen carbonate solution (20 mL), aqueous HCl (10%, 20 mL), and brine (15 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (chloroform: methanol = 0 → 15%) to obtain **5** as colorless oil (67 mg, 59%); R*<sup>f</sup>* 0.16 (chloroform:methanol = 9:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.04 (s, 18 H, <sup>t</sup>Bu), 1.09 (s, 18 H, <sup>t</sup>Bu), 3.14 (d, <sup>2</sup> *J* = 12.8 Hz, 4 H, CH2Ar), 3.34 (s, 6 H, OCH3), 3.37–3.44 (m, 4 H, NCH2), 3.49–3.55 (m, 8 H, OCH2), 3.59–3.71 (m, 12 H, NCH2, OCH2), 3.97 (t, <sup>3</sup> *J* = 5.7 Hz, 4 H, OCH2), 4.18 (t, <sup>3</sup> *J* = 5.7 Hz, 4 H, OCH2), 4.60 (d, <sup>2</sup> *J* = 12.8 Hz, 4 H, CH2Ar), 4.78 (s, 4 H, CH2C=O), 6.74 (s, 4 H, ArH), 6.78 (s, 4 H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 31.5 (CH3), 31.56 (CH3), 31.62 (CH2Ar), 33.9 (Cq), 34.0 (Cq), 42.0 (NCH2), 45.9 (NCH2), 59.1 (OCH3), 66.8 (OCH2), 67.0 (OCH2), 70.1 (OCH2), 70.5 (OCH2), 71.6 (CH2C=O),

72.2 (OCH2), 72.8 (OCH2), 125.2 (CHAr), 125.4 (CHAr), 133.4, 133.9, 144.8, 145.1, 153.1, 153.6 (6 <sup>×</sup> <sup>C</sup>Ar), 168.3 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1130 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(tert-butyl)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]-25**,**27-[2-(1**,**4**,**7 trioxa-10-azacyclododecan-10-yl)-2-oxoethyl]calix[4]arene 6.** Under Ar, compound 3 (100 mg, 0.10 mmol) was dissolved in CCl<sup>4</sup> (5 mL), oxalyl chloride (0.75 g, 5.88 mmol) dropwise added and the reaction mixture stirred at 65 ◦C for 5 h. After cooling to rt, the remaining oxalyl chloride and the solvent were removed under high vacuum and anhydrous DCM (5 mL) added. After cooling the solution to 0 ◦C, 1-aza-12-crown-4 (45 mg, 0.26 mmol) and DIPEA (40 mg, 0.31 mmol) were added to resulting mixture was allowed to come to rt and was stirred at rt overnight. Afterwards, DCM (20 mL) was added and the organic phase washed with saturated hydrogen carbonate solution (15 mL), aqueous HCl (10%, 15 mL), and brine (15 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (chloroform:methanol = 0 → 15%) to obtain **6** as colorless solid (103 mg, 78%); R*<sup>f</sup>* 0.29 (chloroform:methanol = 85:15); <sup>1</sup>H NMR (400 MHz, CDCl3): δ = 1.08 (s, 18 H, <sup>t</sup>Bu), 1.13 (s, 18 H, <sup>t</sup>Bu), 3.26–3.32 (m, 10 H, ArCH2, OCH3), 3.34–3.42 (m, 4 H, CH2), 3.44–3.48 (m, 4 H, CH2), 3.50–3.55 (m, 4 H, CH2), 3.58–3.67 (m, 16 H, CH2), 3.69–3.76 (m, 8 H, CH2), 3.86–3.94 (m, 8 H, CH2), 4.12–4.18 (m, 4 H, CH2), 4.34 (d, 4 H, <sup>2</sup> *J* = 12.5 Hz, CH2Ar), 4.78 (s, 4 H, CH2C=O), 7.05 (s, 4 H, ArH), 7.07 (s, 4 H, ArH) ppm; <sup>13</sup>C NMR (101 MHz, CDCl3): δ = 30.0 (CH2Ar), 31.3 (CH3), 31.4 (CH3), 34.2 (Cq), 34.3 (Cq), 49.3 (CH2), 50.0 (CH2), 59.0 (OCH3), 68.6, 68.8, 69.1, 69.5, 69.9, 70.0, 70.1, 70.9, 72.0 (9 × CH2), 73.9 (CH2C=O), 75.2 (CH2), 125.7 (CHAr), 125.9 (CHAr), 134.6, 134.8, 147.7, 148.3, 148.5, 150.0 (6 × CAr), 170.1 (C=O) ppm.

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]-25**,**27-[2-(trifluoromethylsulfonamido)-2-oxoethyl]calix[4]arene 7a.** Under Ar, compound 3 (100 mg, 0.10 mmol) was dissolved in CCl<sup>4</sup> (5 mL), oxalyl chloride (0.75 g, 5.88 mmol) dropwise added and the reaction mixture stirred at 65 ◦C for 5 h. After cooling to rt, the remaining oxalyl chloride and the solvent were removed under high vacuum, anhydrous DCM (5 mL) added and the solution cooled to 0 ◦C. In a second flask, trifluoromethanesulfonamide (39 mg, 0.26 mmol) was dissolved in anhydrous THF (2 mL) and NaH (41 mg, 1.03 mmol, 10 eq., 60% in mineral oil) was added. After stirring for 15 min, this solution was added to the DCM solution at 0 ◦C and the combined mixture was stirred for 1.5 h at rt. The solvent was changed to chloroform (20 mL) and the organic phase washed with saturated hydrogen carbonate solution (15 mL), aqueous HCl (10%, 15 mL), and brine (15 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (petroleum ether:ethyl acetate = 0 → 30%) to obtain **7a** as colorless solid (68 mg, 54%); mp 113–115 ◦C; R*<sup>f</sup>* 0.76 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.04 (s, 18 H, <sup>t</sup>Bu), 1.20 (s, 18 H, <sup>t</sup>Bu), 3.34 (d, 2 *J* = 12.4 Hz, 4 H, CH2Ar), 3.34 (s, 6 H, OCH3), 3.59 (t, <sup>3</sup> *J* = 4.3 Hz, 4 H, OCH2), 3.69–3.78 (m, 8 H, OCH2), 4.08–4.12 (m, 4 H, OCH2), 4.28 (d, <sup>2</sup> *J* = 12.4 Hz, 4 H, CH2Ar), 4.46 (s, 4 H, CH2C=O), 6.99 (s, 4 H, ArH), 7.15 (s, 4 H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.0 (CH2Ar), 31.2 (CH3), 31.5 (CH3), 34.2 (Cq), 34.3 (Cq), 59.2 (OCH3), 68.7 (OCH2), 70.0 (OCH2), 70.6 (OCH2), 76.4 (OCH2), 76.9 (CH2C=O), 120.5 (q, <sup>1</sup> *J*C,F = 323 Hz, CF3), 125.97 (CHAr), 126.02 (CHAr), 134.3, 134.7, 147.6, 148.4, 148.5, 149.6 (6 <sup>×</sup> <sup>C</sup>Ar), 178.3 (C=O); <sup>19</sup>F NMR (376 MHz, CDCl3): <sup>δ</sup> <sup>−</sup> 79.0 (CF3) ppm; MS (ESI+) *<sup>m</sup>*/*<sup>z</sup>* = 1232 (M<sup>+</sup> + H), 1254 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(tert-butyl)-26**,**28-bis[2-(2-methoxy ethoxy)ethoxy]-25**,**27-[2-(heptafluoroisopropylsulfonamido)-2-oxoethyl]calix[4]arene 7b.** Under Ar, compound 3 (100 mg, 0.10 mmol) was dissolved in CCl<sup>4</sup> (5 mL), oxalyl chloride (0.75 g, 5.88 mmol) dropwise added and the reaction mixture stirred at 65 ◦C for 5 h. After cooling to rt, the remaining oxalyl chloride and the solvent were removed under high vacuum, anhydrous THF (3 mL) added and the solution cooled to 0 ◦C. In a second flask, heptafluoroisopropylsulfonamide (64 mg, 0.26 mmol) was dissolved in anhydrous THF (2 mL) and NaH (41 mg, 1.03 mmol, 60% in mineral oil) was added. After stirring for 15 min, this solution was added to the other THF solution at 0 ◦C and the combined mixture was stirred for 1.5 h at rt. The

solvent was changed to chloroform (20 mL) and the organic phase washed with saturated hydrogen carbonate solution (15 mL), aqueous HCl (10%, 15 mL), and brine (15 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (petroleum ether:ethyl acetate = 0 → 20%) to obtain **7b** as colorless solid (53 mg, 36%); mp 113–115 ◦C; R*<sup>f</sup>* 0.76 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.04 (s, 18 H, <sup>t</sup>Bu), 1.21 (s, 18 H, <sup>t</sup>Bu), 3.35 (d, <sup>2</sup> *J* = 12.5 Hz, 4 H, CH2Ar), 3.41 (s, 6 H, OCH3), 3.58 (t, <sup>3</sup> *J* = 4.4 Hz, 4 H, OCH2), 3.70–3.77 (m, 8 H, OCH2), 4.06–4.11 (m, 4 H, OCH2), 4.27 (d, <sup>2</sup> *J* = 12.5 Hz, 4 H, CH2Ar), 4.44 (s, CH2C=O), 6.99 (s, 4 H, ArH), 7.16 (s, 4 H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 29.9 (CH2Ar), 31.2 (CH3), 31.5 (CH3), 34.2 (Cq), 34.4 (Cq), 59.2 (OCH3), 68.8 (OCH2), 70.0 (OCH2), 70.6 (OCH2), 76.3 (OCH2), 76.9 (CH2C=O), 96.5 (dsep, <sup>1</sup> *J*C,F = 240 Hz, 2 *J*C,F = 32 Hz, CF), 119.6 (dq, <sup>1</sup> *J*C,F = 288 Hz, <sup>2</sup> *J*C,F = 26 Hz, CF3), 126.0 (CHAr), 126.04 (CHAr), 134.3, 134.7, 147.7, 148.5, 148.52, 149.5 (6 <sup>×</sup> <sup>C</sup>Ar), 178.0 (C=O); <sup>19</sup>F NMR (565 MHz, CDCl3): <sup>δ</sup> –170.5 (sep, <sup>3</sup> *<sup>J</sup>* = 7.0 Hz, 1 F, CF), <sup>−</sup>71.9 (d, <sup>3</sup> *J* = 7.0 Hz, 6 F, CF3) ppm.

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-bis[2-(2-methoxyethoxy)ethoxy]-25**,**27-[2-(pentafluorophenylsulfonamido)-2-oxoethyl]calix[4]arene 7c.** Under Ar, compound 3 (100 mg, 0.10 mmol) was dissolved in CCl<sup>4</sup> (5 mL), oxalyl chloride (0.75 g, 5.88 mmol) dropwise added and the reaction mixture stirred at 65 ◦C for 5 h. After cooling to rt, the remaining oxalyl chloride and the solvent were removed under high vacuum, anhydrous THF (3 mL) added and the solution cooled to 0 ◦C. In a second flask, pentafluorophenylsulfonamide (64 mg, 0.26 mmol) was dissolved in anhydrous THF (2 mL) and NaH (41 mg, 1.03 mmol, 60% in mineral oil) was added. After stirring for 15 min, this solution was added to the other THF-solution at 0 ◦C and the combined mixture was stirred for 1.5 h at rt. The solvent was changed to chloroform (20 mL) and the organic phase washed with saturated hydrogen carbonate solution (15 mL), aqueous HCl (10%, 15 mL), and brine (15 mL). After separation, the organic phase was dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (petroleum ether:ethyl acetate = 0 → 20%) to obtain **7c** as colorless solid (15 mg, 10%); mp 98–100 ◦C; R*<sup>f</sup>* 0.76 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 1.06 (s, 18 H, <sup>t</sup>Bu), 1.18 (s, 18 H, <sup>t</sup>Bu), 3.31 (d, <sup>2</sup> *J* = 12.4 Hz, 4 H, ArCH2), 3.39 (s, 6 H, OCH3), 3.51 (t, <sup>3</sup> *J* = 4.6 Hz, 4 H, OCH2), 3.58 (t, 3 *J* = 3.8 Hz, 4 H, OCH2), 3.67 (t, <sup>3</sup> *J* = 4.6 Hz, 4 H, OCH2), 4.02 (t, <sup>3</sup> *J* = 3.8 Hz, 4 H, OCH2), 4.25 (d, <sup>2</sup> *J* = 12.4 Hz, 4 H, CH2Ar), 4.41 (s, 4 H, CH2C=O), 7.00 (s, 4 H, ArH), 7.12 (s, 4 H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 30.0 (CH2Ar), 31.3 (CH3), 31.5 (CH3), 34.2 (Cq), 34.3 (Cq), 59.3 (OCH3), 68.3 (OCH2), 69.7 (OCH2), 70.4 (OCH2), 75.9 (OCH2), 76.9 (CH2C=O), 125.9 (CHAr), 125.94 (CHAr), 134.5, 134.6, 147.7, 148.3, 148.9, 149.5 (6 × Cq), 177.3 (C=O); <sup>19</sup>F NMR (564 MHz, CDCl3): δ –160.7 (t, <sup>3</sup> *J* = 20.0 Hz, 4 F, m-ArF), –150.3 (t, <sup>3</sup> *J* = 20.5 Hz, 2 F, p-ArF), <sup>−</sup>130.1 (d, <sup>3</sup> *J* = 20.0 Hz, 4 F, o-ArF) ppm; MS (ESI+) *m*/*z* = 1428 (M<sup>+</sup> + H), 1445 (M<sup>+</sup> + NH4).

*tert***-Butyl 3**,**4-bis[2-(2-hydroxyethoxy)ethoxy]benzoate 11c.** Under Ar, compound **9c** (176 mg, 0.84 mmol), K2CO<sup>3</sup> (578 mg, 4.19 mmol) and KI (194 mg, 4.2 mmol) were suspended in anhydrous DMF (5 mL) and 2-(2-chloroethoxy)ethanol (354 µL, 417 mg, 3.35 mmol) was added. The mixture was stirred at 75 ◦C overnight. After cooling to rt, the solvent was changed to DCM (15 mL) and filtered. The organic phase was washed with hydrochloric acid (10 mL, 10%), brine (10 mL) and water (10 mL). After removal of the solvent, the crude product was purified via column chromatography (ethyl acetate:methanol 99:1) to obtain **11c** as colorless oil (140 mg, 43%); R*<sup>f</sup>* = 0.4 (DCM:methanol = 9:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.58 (s, 9H, <sup>t</sup>Bu). 2.79 (s, 2H, OH), 3.72–3.65 (m, 4H, OCH2), 3.79–3.71 (m, 4H, OCH2), 3.95–3.88 (m, 4H, OCH2), 4.24–4.17 (m, 4H, OCH2), 6.86 (d, <sup>3</sup> *J* = 8.4 Hz, 1H, ArH), 7.53 (d, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH), 7.60 (dd, <sup>3</sup> *J* = 8.4 Hz, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 28.2 (tBu), 61.6 (OCH2), 68.3 (OCH2), 68.4 (OCH2), 69.0 (OCH2), 69.2 (OCH2), 72.7 (OCH2), 72.8 (OCH2), 80.8 (Cq), 111.7 (CHAr), 113.9 (CHAr), 123.6 (CHAr), 125.0 (CAr), 147.7 (CAr), 151.9 (CAr), 165.5 (C=O) ppm; MS (ESI+): *m*/*z* = 409 (M<sup>+</sup> + Na).

**1**,**2-Bis[2-(2-hydroxyethoxy)ethoxy]-4-nitrobenzene 11d.** Under Ar, 4-nitrocatechol (1.0 g, 6.45 mmol), K2CO<sup>3</sup> (8.0 g, 64 mmol) and KI (1.66 g, 9.03 mmol) were suspended

in anhydrous DMF (20 mL) and 2-(2-chloroethoxy)ethanol (2.72 g, 29mmol) was added. The mixture was stirred at 75 ◦C overnight. After cooling to rt, the solvent was changed to DCM (35 mL) and filtered. The organic phase was washed with hydrochloric acid (25 mL, 10%), brine (25 mL) and water (25 mL). After removal of the solvent, the crude product was purified via column chromatography (DCM:methanol 97:3) to obtain **11d** as colorless oil (1.08 g, 52%); R*<sup>f</sup>* 0.4 (DCM:methanol 9:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 3.41 (s, 2H, OH), 3.63–3.59 (m, 4H, OCH2), 3.69–3.66 (m, 4H, OCH2), 3.90–3.84 (m, 4H, OCH2), 4.20–4.12 (m, 4H, OCH2), 6.85 (d, <sup>3</sup> *J* = 8.9 Hz, 1H, ArH), 7.67 (d, <sup>4</sup> *J* = 2.6 Hz, 1H, ArH), 7.80 (dd, <sup>3</sup> *J* = 8.9 Hz, 4 *J* = 2.6 Hz, 1H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 61.4 (OCH2), 61.5 (OCH2), 68.6 (OCH2), 68.7 (OCH2), 68.8 (OCH2), 68.9 (OCH2), 72.7 (OCH2), 72.7 (OCH2), 108.0 (CHAr), 111.3 (CHAr), 118.0 (CHAr), 141.4 (CAr), 148.0 (CAr), 153.9 (CAr) ppm; MS (ESI+): *m*/*z* = 354 (M<sup>+</sup> + Na).

*tert***-Butyl 3**,**4-bis{2-[2-(tosyloxy)ethoxy]ethoxy}benzoate 12c.** Under Ar, compound **11c** (459 mg, 1.2 mmol) and Et3N (536 µL, 392 mg, 3.87 mmol) were dissolved in anhydrous DCM (15 mL), cooled to 0 ◦C, *p*-TsCl (1.40 g, 9.9 mmol) added and the reaction mixture stirred at rt overnight. Afterwards, the organic phase was washed with water (2 × 15 mL), dried over Na2SO4. After removal of the solvent, the crude product was purified using automated column chromatography (DCM → DCM:methanol 99:1) to obtain **12c** as colorless oil (298 mg, 36%); R*<sup>f</sup>* 0.6 (DCM:methanol = 99:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.59 (s, 9H, <sup>t</sup>Bu), 2.42–2.39 (m, 6H, CH3), 3.85–3.73 (m, 8H, OCH2), 4.15–4.05 (m, 4H, OCH2), 4.21–4.14 (m, 4H, OCH2), 6.84 (d, <sup>3</sup> *J* = 8.4 Hz, 1H, ArH), 7.32–7.25 (m, 4H, ArTs), 7.48 (d, 4 *J* = 2.0 Hz, 1H, ArH), 7.60 (dd, <sup>3</sup> *J* = 8.4 Hz, <sup>4</sup> *J* = 2.0 Hz, 1H, ArH), 7.78 (d, <sup>3</sup> *J* = 8.0 Hz, 4H, ArTs); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 21.6 (CH3), 21.6 (CH3), 28.2 (tBu), 68.6 (OCH2), 68.8 (OCH2), 68.9 (OCH2), 69.0 (OCH2), 69.3 (OCH2), 69.4 (OCH2), 69.6 (OCH2), 69.8 (OCH2), 80.8 (Cq), 112.6 (CHAr), 114.8 (CHAr), 123.8 (CHAr), 125.1 (CAr), 128.0 (CHTs), 129.8 (CHTs), 133.0, 144.8, 148.1, 152.4 (4 <sup>×</sup> <sup>C</sup>Ar), 165.5 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* 718 (M<sup>+</sup> + Na).

**1**,**2-Bis{2-[2-(tosyloxy)hydroxyethoxy]ethoxy}-4-nitrobenzene 12d.** Compound **11d** (1.37 g, 4,13 mmol) was dissolved in THF and cooled to 0 ◦C. NaOH (500 mg, 12.4 mmol) dissolved in water (2.5 mL) and *p*-tosyl chloride (1.97 g, 10.3 mmol) were added and the mixture was stirred 3 h at rt. Afterwards, saturated hydrogen carbonate solution (10 mL) was added and extracted with DCM (2 × 50 mL). The organic phase was washed with water (2 × 50 mL), dried over Na2SO<sup>4</sup> and the crude product was purified using automated column chromatography (DCM → DCM:methanol 50:1) to obtain **12d** as yellowish oil (1.74 g, 66%); R*<sup>f</sup>* 0.6 (DCM:methanol = 99:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 2.42–2.40 (m, 6H, CH3), 3.79–3.76 (m, 4H, OCH2), 3.87–3.81 (m, 4H, OCH2), 4.15–4.11 (m, 2H, OCH2), 4.20–4.15 (m, 6H, OCH2), 6.91 (d, <sup>3</sup> *J* = 8.9 Hz, 1H, ArH), 7.32–7.28 (m, 4H, Ts), 7.73 (d, 4 *J* = 2.6 Hz, 1H, ArH), 7.80–7.75 (m, 4H, Ts), 7.88 (dd, <sup>3</sup> *J* = 8.9 Hz, <sup>4</sup> *J* = 2.6 Hz, 1H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 21.7 (CH3), 21.8 (CH3), 69.1 (OCH2), 69.2 (OCH2), 69.2 (OCH2), 69.3 (OCH2), 69.4 (OCH2), 69.5 (OCH2), 69.6 (CH2), 69.7 (OCH2), 109.0 (CHAr), 112.1 (CHAr), 118.3 (CHAr), 128.1 (CHTs), 128.2 (CHTs), 129.9 (CHTs), 130.0 (CHTs), 133.1, 141.7, 145.0, 145.1, 148.5, 154.5 (6 <sup>×</sup> <sup>C</sup>Ar) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 662 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-dihydroxycalix[4]arene-propylenecrown-6 14b.** Under Ar, *tert*-butylcalix[4]arene (**13**, 158 mg, 0.24 mmol) and K2CO<sup>3</sup> (39 mg, 0.28 mmol) were suspended in DCM (10 mL) and compound **8b** (273 mg, 0.49 mmol) dissolved in 5 mL of DCM was added dropwise. The resulting mixture was stirred at 30 ◦C for 11 d. Afterwards, the DCM phase was washed with water (2 × 15 mL) and aqueous HCl (10%, 2 × 15 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified via column chromatography (petroleum ether:ethyl acetate = 2:1 → 1:1) yielding compound **14b** as a colourless solid (85 mg, 40%); R*<sup>f</sup>* 0.2 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.94 (s, 18H, <sup>t</sup>Bu), 1.30 (s, 18H, <sup>t</sup>Bu), 1.76 (p, 3 *J* = 5.8 Hz, 2H, OCH2), 3.30 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, CH2Ar), 3.67 (t, <sup>3</sup> *J* = 5.8 Hz, 4H, OCH2), 3.75–3.78 (m, 4H, OCH2), 3.90–3.93 (m, 4H, OCH2), 4.00–4.03 (m, 4H, OCH2), 4.13–4.16 (m, 4H, OCH2), 4.37 (d, <sup>2</sup> *J* = 13.0 Hz, 4 H, CH2Ar), 6.78 (s, 4H ArH), 7.06 (s, 4H, ArH), 7.18 (s, 2H, OH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.4 (OCH2), 31.1 (CH3), 31.6 (CH2Ar), 31.9 (CH3),

34.0 (Cq), 34.1 (Cq), 67.5 (OCH2), 71.0 (OCH2), 70.1 (OCH2), 71.3 (OCH2), 76.1 (OCH2), 125.1 (CHAr), 125.6 (CHAr), 128.0 (CAr), 132.7 (CAr), 141.4 (CAr), 146.9 (CAr), 150.0 (CAr), 150.8 (CAr) ppm; MS (ESI+): *m*/*z* = 883 (M<sup>+</sup> + NH4), 888 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-dihydroxycalix[4]arene-benzocrown-6 14c.** Under Ar, *tert*-butylcalix[4]arene (**13**, 610 mg, 0.94 mmol) and K2CO<sup>3</sup> (150 mg, 1.08 mmol) were suspended in DCM (20 mL) and compound **12a** (1.12 g, 1.88 mmol) dissolved in 10 mL of DCM was added dropwise. The resulting mixture was stirred at 30 ◦C for 11 d. Afterwards, the DCM phase was washed with water (2 × 30 mL) and aqueous HCl (10%, 2 × 30 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified via column chromatography (DCM:ethyl acetate = 20:1 → 10:1) yielding compound **14c** as colourless solid (346 mg, 41%); mp 154 ◦C; R*<sup>f</sup>* 0.2 (DCM:methanol = 96:4); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.93 (s, 18H, <sup>t</sup>Bu), 1.29 (s, 18H, <sup>t</sup>Bu), 3.29 (d, <sup>2</sup> *J* = 13.1 Hz, 4H, CH2Ar), 4.11 (t, <sup>3</sup> *J* = 4.7 Hz, 4H, OCH2), 4.15 (t, <sup>3</sup> *J* = 4.7 Hz, 4H, OCH2), 4.23 (t, <sup>3</sup> *J* = 4.7 Hz, 4H, OCH2), 4.27–4.33 (m, 8H, OCH2, CH2Ar), 6.77 (s, 4H, ArH), 6.91–6.94 (m, 2H, ArH), 6.97 (m, 2H, ArH), 7.05 (s, 4H, ArH), 7.18 (s, 2H, OH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 31.1 ( <sup>t</sup>Bu), 31.6 (CH2Ar), 31.9 (tBu), 34.0 (Cq), 34.1 (Cq), 70.3 (OCH2), 70.5 (OCH2), 71.1 (OCH2), 76.5 (OCH2), 116.5 (CHAr), 122.2 (CHAr), 125.1 (CHAr), 125.7 (CHAr), 127.9, 132.6, 141.5, 147.1, 149.5, 149.9, 150.8 (7 <sup>×</sup> <sup>C</sup>Ar) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 917 (M<sup>+</sup> + NH4), 922 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-dihydroxycalix[4]arene-benzocrown-8 14d.** Under Ar, *tert*-butylcalix[4]arene (**13**, 265 mg, 0.41 mmol) and K2CO<sup>3</sup> (65 mg, 0.47 mmol) were suspended in DCM (20 mL) and compound **12b** (557 mg, 0.82 mmol) dissolved in 5 mL of DCM was added dropwise. The resulting mixture was stirred at 30 ◦C for 11 d. Afterwards, the DCM phase was washed with water (2 × 20 mL) and aqueous HCl (10%, 2 × 20 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified via column chromatography (petroleum ether:acetone = 3:1) yielding compound **14d** as colourless solid (325 mg, 81%); R*<sup>f</sup>* 0.2 (petroleum ether:acetone = 3:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.95 (s, 18H, <sup>t</sup>Bu), 1.29 (s, 18H, <sup>t</sup>Bu), 3.28 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, CH2Ar), 3.91–3.96 (m, 8H, OCH2), 3.97–4.05 (m, 8H, OCH2), 4.10–4.16 (m, 8H, OCH2), 4.35 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, CH2Ar), 6.78 (s, 4H, ArH), 6.85–6.91 (m, 4H, ArH), 7.05 (s, 4H, ArH), 7.30 (s, 2H, OH) ppm; <sup>13</sup>C NMR (101 MHz, CDCl3): δ 31.2 (CH3), 31.6 (CH2Ar), 31.9 (CH3), 34.0 (Cq), 34.1 (Cq), 69.6 (OCH2), 70.1 (OCH2), 70.4 (OCH2), 71.4 (OCH2), 71.5 (OCH2), 76.1 (OCH2), 114.2 (CHAr), 121.5 (CHAr), 125.1 (CHAr), 125.6 (CHAr), 127.9, 132.8, 141.4, 147.0, 149.2, 149.9, 150.9 (7 <sup>×</sup> <sup>C</sup>Ar) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1009 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-dihydroxycalix[4]arene-4-***tert***-butoxycarbonyl-benzocrown-6 14e**. Under Ar, *tert*-butylcalix[4]arene (**13**, 140 mg, 0.22 mmol) and K2CO<sup>3</sup> (34 mg, 0.25 mmol) were suspended in DCM (10 mL). Compound **12e** (298 mg, 0.43 mmol) dissolved in 5 mL of DCM was added dropwise. The resulting mixture was stirred at 30 ◦C for 11 d. Afterwards, the DCM phase was washed with water (2 × 20 mL) and aqueous HCl (10%, 2 × 20 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified via column chromatography (petroleum ether:acetone = 4:1 → 1:1) yielding compound **14e** as colourless solid (78 mg, 36%); R*<sup>f</sup>* 0.5 (petroleum ether:acetone = 2:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.93 (s, 18H, <sup>t</sup>Bu), 1.30 (s, 18H, <sup>t</sup>Bu), 1.58 (s, 9H, O <sup>t</sup>Bu), 3.30 (d, <sup>2</sup> *J* = 12.7 Hz, 4H, CH2Ar), 4.10–4.33 (m, 20H, OCH<sup>2</sup> + CH2Ar), 6.76 (s, 4H, ArH), 6.90 (d, <sup>3</sup> *J* = 8.1 Hz, 1H, ArH), 7.05 (s, 4H, ArH), 7.14 (s, 2H, OH), 7.59–7.64 (m, 2H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 28.4 (OtBu), 31.6 (CH2Ar), 31.1 (CH3), 31.9 (CH3), 34.0 (Cq), 34.0 (Cq), 69.8 (OCH2), 70.3 (OCH2), 70.5 (OCH2), 70.6 (OCH2), 70.8 (OCH2), 76.4 (OCH2), 76.5 (OCH2), 80.8 (OCq), 114.0 (CHAr), 116.9 (CHAr), 124.4 (CHAr), 125.1 (CHAr), 125.2 (CHAr), 125.7 (CHAr), 126.1, 127.8, 127.9, 132.6, 141.8, 141.9, 147.0, 147.1, 148.5, 150.8, 153.8 (11 <sup>×</sup> <sup>C</sup>Ar), 165.7 C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1022 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-26**,**28-dihydroxycalix[4]arene-4-nitrobenzocrown-6 14f.** Under Ar, *tert*-butylcalix[4]arene (**13**, 882 mg, 1.36 mmol) and K2CO<sup>3</sup> (220 mg, 1.56 mmol) were suspended in DCM (20 mL), and compound **12f** (1.74 g, 2.72 mmol) dissolved in 10 mL of DCM was added dropwise. The resulting mixture was stirred at 30 ◦C for 11 d. Afterwards, the DCM phase was washed with water (2 × 30 mL) and aqueous HCl (10%,

2 × 30 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified via column chromatography (DCM:ethyl acetate = 97:3 → 9:1) yielding compound **14f** as colourless solid (870 mg, 68%); R*<sup>f</sup>* 0.3 (DCM:ethyl acetate = 9:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.91 (s, 18H, CH3), 1.29 (s, 18H, CH3), 3.25–3.30 (m, 4H, ArCH2), 4.08–4.15 (m, 8H, OCH2, ArCH2), 4.18–4.30 (m, 8H, OCH2), 4.34–4.40 (m, 4H, OCH2), 6.71–6.76 (m, 4H, ArH), 6.88–6.92 (m, 1H, ArH), 6.99 (s, 2H, OH), 7.02–7.04 (m, 4H, ArH), 7.77–7.83 (m, 2H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 31.1 (tBu), 31.5 (ArCH2), 31.9 (tBu), 34.0 (Cq), 34.1 (Cq), 69.9 (OCH2), 70.3 (OCH2), 70.4 (OCH2), 70.5 (OCH2), 70.6 (OCH2), 70.8 (OCH2), 76.2 (OCH2), 76.3 (OCH2), 110.5 (CHAr), 113.3 (CHAr), 118.5 (CHAr), 125.1 (CHAr), 125.2 (CHAr), 125.7 (CHAr), 127.8, 127.9, 132.4, 132.5, 141.6, 141.9, 147.1, 149.8, 149.9, 150.7, 154.9 ppm (11 <sup>×</sup> <sup>C</sup>Ar); MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 967 (M<sup>+</sup> + Na), 983 (M<sup>+</sup> + K).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)calix[4]arene-propylenecrown-6 15b.** Under Ar, compound **14b** (85 mg, 0.12 mmol) was dissolved in anhydrous THF (10 mL) and NaH (23 mg, 0.58 mmol, 60% in mineral oil) was added and the mixture stirred for 30 min at rt. Next, ethyl bromoacetate (65 µL, 0.58 mmol) was added and the mixture stirred at 60 ◦C overnight. Afterwards, the solvent was changed to DCM (15 mL), the organic phase washed with water (2 × 15 mL) and dried over Na2SO4. After removal of the solvent, the crude product was purified via column chromatography (petroleum ether:ethyl acetate = 2:1 → 1:1) yielding compound **15b** as colourless solid (45 mg, 37%); R*<sup>f</sup>* 0.2 (petroleum ether:ethyl acetate = 2:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.88 (s, 18H, <sup>t</sup>Bu), 1.26 (s, 18H, <sup>t</sup>Bu), 1.30 (t, <sup>3</sup> *J* = 7.1 Hz, 6H, CH3), 1.83 (p, <sup>3</sup> *J* = 5.7 Hz, 2H, CH2), 3.16 (d, 2 *J* = 12.7 Hz, 4H, CH2Ar), 3.67 (t, <sup>3</sup> *J* = 5.7 Hz, 4H, OCH2), 3.70 (m, 4H, OCH2), 3.75–3.78 (m, 4H, OCH2), 4.11–4.15 (m, 4H, OCH2), 4.21–4.28 (m, 8H, CH2C=O, OCH2), 4.51 (d, 2 *J* = 12.7 Hz, 4H, CH2Ar), 6.55 (s, 4H, ArH), 4.56 (s, 4H, OCH2), 7.02 (s, 4H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 14.4 (CH3), 30.5 (CH2), 31.3 (CH3), 31.4 (CH2Ar), 31.8 (CH3), 33.8 (Cq), 34.2 (Cq), 60.8 (CH 3 CH 2 OCO), 67.1 (OCH2), 70.0 (OCH2), 70.1 (OCH2), 70.4 (OCH2), 72.1 (OCH2C=O), 72.7 (OCH2), 125.0 (CHAr), 125.6 (CHAr), 132.4, 135.1, 145.0, 145.2, 152.3, 154.3 (6 <sup>×</sup> <sup>C</sup>Ar), 169.9 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1060 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)calix[4]arene-benzocrown-6 15c.** Under Ar, compound **14c** (346 mg, 0.39 mmol) was dissolved in anhydrous THF (20 mL) and NaH (77 mg, 1.93 mmol, 60% in mineral oil) was added and the mixture stirred for 30 min at rt. Next, ethyl bromoacetate (214 µL, 1.93 mmol) and NaI in catalytic amounts were added and the mixture stirred at 60 ◦C overnight. Afterwards, the solvent was changed to DCM (20 mL), the organic phase was washed with water (2 × 20 mL) and dried over Na2SO4. After removal of the solvent, the product was recrystallized from hot methanol. After filtration the product was washed with cold methanol yielding compound **15c** as colorless solid (238 mg, 58%); R*<sup>f</sup>* 0.2 (petroleum ether: ethyl acetate = 2:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.92 (s, 18H, CH3), 1.14 (t, <sup>3</sup> *J* = 7.1 Hz, 6H, CH3), 1.23 (s, 18H, CH3), 3.17 (d, <sup>2</sup> *J* = 12.7 Hz, 4H, ArCH2), 4.00–4.07 (m, 8H, OCH2, CH2), 4.19–4.28 (m, 12H, OCH2), 4.54 (d, <sup>2</sup> *J* = 12.7 Hz, 4H, ArCH2), 4.61 (s, 4H, CH2C=O), 6.58 (s, 4H, ArH), 6.91 (s, 4H, ArH), 6.97 (s, 4H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 28.1 (CH3), 31.2 (ArCH2), 31.3 (tBu), 31.7 ( <sup>t</sup>Bu), 33.8 (Cq), 34.1 (Cq), 69.4 (OCH2), 70.2 (OCH2), 70.9 (OCH2), 72.0, (CH2C=O), 77.4 (OCH2), 114.6 (CHAr), 121.6 (CHAr), 123.6 (CHAr), 125.1 (CHAr), 125.6 (CHAr), 128.2, 132.6, 134.7, 145.1, 149.6, 149.6 (6 <sup>×</sup> <sup>C</sup>Ar), 170.0 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1094 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)calix[4]arene-benzocrown-8 15d.** Under Ar, compound **14d** (325 mg, 0.33 mmol) was dissolved in anhydrous THF (20 mL) and NaH (184 mg, 1.7 mmol, 60% in mineral oil) was added and the mixture stirred for 30 min at rt. Next, ethyl bromoacetate (183 µL, 1.7 mmol) and NaI in catalytic amounts were added and the mixture stirred at 60 ◦C overnight. Afterwards, the solvent was changed to DCM (15 mL), the organic phase was washed with brine (2 × 15 mL) and dried over Na2SO4. After removal of the solvent, the crude product was purified via column chromatography (DCM:methanol = 95:5) yielding compound **15d** as colorless solid (170 mg, 45%); R*<sup>f</sup>* 0.2 (petroleum ether:ethyl acetate = 2:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.87 (s, 18H, CH3), 1.23–1.28 (m, 24H, CH<sup>3</sup> + OCH2CH3), 3.15 (d, <sup>2</sup> *J* = 12.7 Hz, 4H, ArCH2),

3.79–3.82 (m, 4H, OCH2), 3.87–3.90 (m, 4H, OCH2), 3.94 (t, <sup>3</sup> *J* = 4.5 Hz, 4H, OCH2CH3), 4.10–4.33 (m, 16H, OCH2), 4.48 (d, <sup>2</sup> *J* = 12.7 Hz, 4H, ArCH2), 4.52 (s, 4H, CH2C=O), 6.53 (s, 4H, ArH), 6.88–6.92 (m, 4H, ArH), 7.02 (m, 4H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 14.4 (CH3), 31.3 (tBu), 31.6 (ArCH2), 31.8 (tBu), 60.9 (CH2), 69.6 (OCH2), 69.9 (OCH2), 70.0 (OCH2), 70.8 (OCH2), 71.2 (OCH2), 72.2 (CH2C=O), 72.5 (OCH2), 77.4 (OCH2), 114.3 (CHAr), 121.6 (CHAr), 125.1 (CHAr), 125.6 (CHAr), 132.3, 135.1, 145.0, 145.2, 149.2, 152.3, 154.4 (7 <sup>×</sup> <sup>C</sup>Ar), 169.9 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1182 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)calix[4]arene-4-***tert***-butoxycarbonyl-benzocrown-6 15e.** Under Ar, compound **14e** (78 mg, 0.078 mmol) was dissolved in anhydrous THF (10 mL) and NaH (16 mg, 0.39 mmol, 60% in mineral oil) was added and the mixture stirred for 30 min at rt. Next, ethyl bromoacetate (44 µL, 0.39 mmol) and NaI in catalytic amounts were added and the mixture stirred at 60 ◦C overnight. Afterwards, the solvent was changed to DCM (15 mL), the organic phase was washed with brine (2 × 15 mL) and dried over Na2SO4. After removal of the solvent, the crude product was purified via column chromatography (petroleum ether:ethyl acetate = 4:1) yielding compound **15e** as colorless solid (31 mg, 34%); R*<sup>f</sup>* 0.2 (petroleum ether:ethyl acetate = 2:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.93 (s, 18H, CH3), 1.12 (t, <sup>3</sup> *J* = 7.2 Hz, 6H, CH2CH3), 1.21 (s, 18H, CH3), 1.58 (s, 9H, OtBu), 3.17 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 3.97–4.07 (m, 8H, OCH2), 4.20–4.29 (m, 12H, OCH2), 4.50–4.58 (m, 4H, ArCH2), 4.62 (s, 4H, CH2C=O), 6.59 (s, 4H, ArH), 6.86 (d, 3 *J* = 8.5 Hz, 1H, ArH), 6.95 (s, 4H, ArH), 7.52 (s, 1H, ArH), 7.60 (d, <sup>3</sup> *J* = 8.5 Hz, 1H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 14.2 (CH2CH3), 28.4 (OtBu), 31.4 (tBu), 31.5 (ArCH2), 31.7 ( <sup>t</sup>Bu), 33.9 (Cq), 34.1 (Cq), 60.7 (CH2CH3), 69.2 (OCH2), 69.6 (OCH2), 70.0 (OCH2), 70.1 (OCH2), 71.1 (OCH2), 71.2 (OCH2), 71.9 (CH2C=O), 73.5 (OCH2), 80.8 (COOC(CH3)3), 112.4 (CHAr), 115.0 (CHAr), 123.8 (CHAr), 124.9 (CAr), 125.1 (CHAr), 125.1 (CHAr), 125.6 (CHAr), 132.7, 134.6, 134.6, 145.1, 148.6, 152.2, 153.1, 154.5, 154.6 (9 × CAr), 165.7 (C=O), 170.0 (C=O) ppm; MS (ESI+): *m*/*z* = 1195 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(2-ethoxy-2-oxoethoxy)calix[4]arene-4-nitrobenzocrown-6 15f.** Under Ar, compound **14f** (870 mg, 0.92 mmol) was dissolved in anhydrous THF (40 mL) and NaH (184 mg, 4.61 mmol, 60% in mineral oil) was added and the mixture stirred for 30 min at rt. Next, ethyl bromoacetate (513 µL, 1.93 mmol) and NaI in catalytic amounts were added and the mixture stirred at 60 ◦C overnight. Afterwards, the solvent was changed to DCM (30 mL), the organic phase was washed with brine (2 × 30 mL) and dried over Na2SO4. After removal of the solvent, the crude product was purified via column chromatography (DCM → DCM:methanol = 98:2) yielding compound **15f** as colorless solid (960 mg, 93%); R*<sup>f</sup>* 0.5 (DCM:methanol = 95:5); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.95 (s, 18H, CH3), 1.11 (t, <sup>3</sup> *J* = 7.1 Hz, 6H, CH2CH3), 1.19 (br. s, 18H, CH3), 3.17 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 3.98–4.03 (m, 4H, CH2CH3), 4.04–4.09 (m, 4H, OCH2), 4.20–4.30 (m, 12H, OCH2), 4.50–4.58 (m, 4H, ArCH2), 4.65 (s, 4H, OCH2), 6.62 (s, 4H, ArH), 6.91–6.94 (m, 1H, ArH), 6.93 (d, <sup>3</sup> *J* = 8.9 Hz, 4H, ArH), 7.75 (d, <sup>4</sup> *J* = 2.7 Hz, 1H, ArH), 7.90 (dd, <sup>3</sup> *J* = 8.9 Hz, <sup>4</sup> *J* = 2.7 Hz, 1H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 14.2 (CH2CH3). 31.4 (tBu), 31.7 (ArCH2), 31.8 (tBu), 33.9 (Cq), 34.2 (Cq), 60.7 (CH2CH3), 69.8 (OCH2), 69.9 (OCH2), 70.0 (OCH2), 71.3 (OCH2), 71.4 (OCH2), 72.0 (OCH2CO), 73.4 (OCH2), 73.5 (OCH2), 109.2 (CHAr), 112.1 (CHAr), 118.1 (CHAr), 125.1 (CHAr), 125.2 (CHAr), 125.7 (CHAr), 132.8, 134.5, 134.6, 141.9, 145.2, 145.3, 152.4, 154.6, 154.7, 155.1 (10 × CAr), 169.9 (C=O) ppm; MS (ESI+): *m*/*z* = 1139 (M<sup>+</sup> + Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(carboxymethoxy)calix[4]arene-propylenecrown-6 16b.** Compound **15b** (45 mg, 43 µmol) was dissolved in THF (5 mL), a solution of Me4NOH · 5 H2O (55 mg, 0.30 mmol) in methanol (2 mL) was added and the reaction mixture was stirred at 55 ◦C overnight. The major part of the solvent was removed and the product was precipitated with ice-cold aqueous HCl (6 M). The solid residue was filtered and washed with water (20 mL) and dissolved in DCM (10 mL). The organic phase was washed with cold water (5 mL). After separation, the organic phase was dried over Na2SO4, the solvent was removed and **16b** was obtained as grey solid (41 mg, 95%); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 0.83 (s, 18H, <sup>t</sup>Bu), 1.33 (s, 18H, <sup>t</sup>Bu), 1.67 (p, <sup>3</sup> *J* = 6.7 Hz, 2H, CH2), 3.21 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, CH2Ar), 3.58 (t, <sup>3</sup> *J* = 6.7 Hz, 4H, OCH2), 3.65–3.68 (m, 4H, OCH2), 3.72–3.75 (m, 4H, OCH2), 3.83–3.86 (m, 4H, OCH2), 3.96–4.01 (m, 4H, OCH2), 4.50 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, CH2), 4.86 (s, 4H, CH2C=O), 6.59 (s, 4H, ArH), 7.14 (s, 4H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ = 29.8 (CH2); 31.0 (CH2Ar), 31.1 (CH3), 31.8 (CH3), 33.9 (Cq), 34.3 (Cq), 67.3 (OCH2), 70.3 (OCH2), 70.6 (OCH2), 70.7 (OCH2), 72.9 (CH2C=O), 77.1 (OCH2), 125.5 (CHAr), 126.1 (CHAr), 132.6, 135.2, 146.0, 146.9, 150.6, 153.4 (6 × CAr), 171.0 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1048 (M<sup>+</sup> <sup>−</sup> 2 H + 3 Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(carboxymethoxy)calix[4]arene-benzocrown-6 16c.** Compound **15c** (446 mg, 0.435 mmol) was dissolved in THF (20 mL), a solution of Me4NOH · 5 H2O (2.45 g, 6.85 mmol) in methanol (5 mL) was added and the reaction mixture was stirred at 55 ◦C overnight. After filtration, the major part of the solvent was removed and the product was precipitated with ice-cold aqueous HCl (6 M). The solid residue was filtered and washed with water (20 mL) and dissolved in DCM (30 mL). The organic phase was washed with cold water (15 mL). After separation, the organic phase was dried over Na2SO4, the solvent was removed and **16c** was obtained as brownish solid (440 mg, >99%); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.83 (s, 18H, CH3), 1.31 (s, 18H, CH3), 3.19 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 3.80–4.28 (m, 16H, OCH2), 4.45 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 4.86 (s, 4H, OCH2CO), 6.60 (s, 4H, ArH), 6.75–6.88 (m, 4H, ArH), 7.12 (s, 4H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.9 (ArCH2), 31.1 (tBu), 31.8 (tBu), 33.9 (Cq), 34.3 (Cq), 67.9 (OCH2), 70.7 (OCH2), 71.0 (OCH2), 72.9 (OCH2C=O), 77.4 (OCH2), 111.5 (CHAr), 120.6 (CHAr), 125.5 (CHAr), 126.0 (CHAr), 132.6, 135.2, 145.9, 146.9, 148.4, 150.5 (6 × CAr), 170.1 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1060 (M<sup>+</sup> <sup>−</sup> H + 2 Na), 1082 (M<sup>+</sup> <sup>−</sup> 2 H + 3 Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(carboxymethoxy)calix[4]arene-benzocrown-8 16d.** Compound **15d** (170 mg, 0.15 mmol) was dissolved in THF (10 mL), a solution of Me4NOH · 5 H2O (186 mg, 1.03 mmol) in methanol (2 mL) was added and the reaction mixture was stirred at 55 ◦C overnight. After filtration, the major part of the solvent was removed and the product was precipitated with ice-cold aqueous HCl (6 M). The solid residue was filtered and washed with water (10 mL) and dissolved in DCM (30 mL). The organic phase was washed with cold water (15 mL). After separation, the organic phase was dried over Na2SO4, the solvent was removed and **16d** was obtained as brownish solid (134 mg, 83%); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.83 (s, 18H, CH3), 1.33 (s, 18H, CH3), 3.17 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, ArCH2), 3.72–3.75 (m, 4H, OCH2), 3.78–3.84 (m, 8H, OCH2), 3.86–3.90 (m, 4H, OCH2), 3.95–4.04 (m, 8H, OCH2), 4.46 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, ArCH2), 4.74 (s, 4H, OCH2CO), 6.56 (s, 4H, ArH), 6.71–6.76 (m, 2H, ArH), 6.81–6.85 (m, 2H, ArH), 7.12 (s, 4H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.9 (ArCH2), 31.1 (tBu), 31.8 (tBu), 33.9 (Cq), 34.3 (Cq), 69.1 (OCH2), 70.1 (OCH2), 70.5 (OCH2), 71.1 (OCH2), 72.4 (OCH2CO), 77.4 (OCH2), 115.2 (CHAr), 121.6 (CHAr), 125.5 (CHAr), 126.1 (CHAr), 132.5, 135.2, 147.1, 149.1, 150.4, 153.2 (6 <sup>×</sup> <sup>C</sup>Ar), 170.6 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1170 (M<sup>+</sup> <sup>−</sup> 2 H + 3 Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(carboxymethoxy)calix[4]arene-4-***tert***-butylcarboxy-benzocrown-6 16e.** Compound **15e** (31 mg, 27 µmol) was dissolved in THF (4 mL), a solution of Me4NOH · 5 H2O (34 mg, 0.19 mmol) in methanol (2 mL) was added and the reaction mixture was stirred at 55 ◦C overnight. The solvent was removed and the crude product was dissolved in DCM (30 mL). The organic phase was washed with saturated NH4Cl solution (15 mL) and water (15 mL). After separation, the organic phase was dried over Na2SO4, the solvent was removed and **16e** was obtained as yellowish oil (26 mg, 87%); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.83 (s, 18H, CH3), 1.31 (s, 18H, CH3), 1.56 (s, 9H, OC(CH3)3), 3.19 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 3.83–4.08 (m, 12H, OCH2), 4.26–4.31 (m, 4H, OCH2), 4.44 (d, <sup>3</sup> *J* = 12.8 Hz, 4H, ArCH2), 4.84 (s, 4H, OCH2CO), 6.60 (s, 4H, ArH), 6.76 (d, <sup>3</sup> *J* = 8.5 Hz, 1H, ArH), 6.98 (s, 4H, ArH), 7.40 (d, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH), 7.55 (dd, <sup>3</sup> *J* = 8.5 Hz, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 28.4 (OtBu), 31.1 (tBu), 31.2 (ArCH2), 31.8 (tBu), 33.9 (Cq), 34.3 (Cq), 68.2 (OCH2), 68.5 (OCH2), 70.4 (OCH2), 70.5 (OCH2), 70.9 (OCH2), 71.0 (OCH2), 72.0 (OCH2CO), 77.4 (OCH2), 80.6 (OCq), 110.6 (CHAr), 112.2 (CHAr), 123.2 (CHAr), 125.3 (CAr), 125.5 (CHAr), 125.7 (CHAr), 135.2, 136.0, 143.3, 145.8, 145.9, 147.0, 147.9, 150.4, 150.5, 151.7, 152.1 (11 <sup>×</sup> <sup>C</sup>Ar), 165.9 (COOtBu), 172.8 (C=O) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1160 (M<sup>+</sup> <sup>−</sup> H + 2 Na).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-heptafluoropropane-2-sulfonylcarbamoyl-methoxy)calix[4]arene-crown-6 21.** Calixarene **16a** (300 mg, 0.31 mmol) was suspended in CCl<sup>4</sup> (6 mL), oxalyl chloride (1.5 mL) was added and the mixture was stirred for 5 h at 65 ◦C. After cooling to rt, the solvent and remaining oxalyl chloride was removed. Under argon, the residue was dissolved in anhydrous DCM (5 mL) and a mixture of perfluoroisopropanesulfonamide (193 mg, 0.77 mmol) and NaH (60% in mineral oil, 124 mg, 3.1 mmol) dissolved in anhydrous DCM was added. After stirring overnight at rt, the mixture was filtered, the organic phase was washed with 10% HCl, the organic phase was separated and dried over Na2SO4. Next, the solvent was removed and the crude product was purified by column chromatography (DCM → DCM/methanol 5:1) to yield calixarene **21** as colorless solid (254 mg, 57%). R*<sup>f</sup>* 0.6 (petroleum ether:ethyl acetate = 2:1); <sup>1</sup>H NMR (600 MHz, CDCl3): δ 1.11 (s, 18H, <sup>t</sup>Bu), 1.15 (s, 18H, <sup>t</sup>Bu), 3.38 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, ArCH2), 3.71–3.74 (m, 4H, OCH2), 3.82–3.86 (m, 4H, OCH2), 3.86–3.92 (s, 8H, OCH2), 4.10–4.18 (m, 8H, OCH2+ArCH2), 4.63 (s, 4H, CH2C=O), 7.08 (s, 4H, *m*-HAr), 7.11 (s, 4H, *m*-HAr); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 30.1 (ArCH2), 31.3, 31.4 (2 x CH3), 34.1, 34.3 (Cq), 69.3, 69,4, 72.1, 72.2, (4 × OCH2), 77.0 (CH2C=O), 78.8 (OCH2), 125.8, 126.3 (2 × *m*-CAr), 134.1, 134.4 (2 <sup>×</sup> *<sup>o</sup>*-CAr), 147.8, 148.4 (2 <sup>×</sup> *<sup>p</sup>*-CAr), 148.3, 151.5 (2 <sup>×</sup> *<sup>i</sup>*-CAr), 176.2 (C=O); <sup>19</sup>F NMR (565 MHz, CDCl3): <sup>δ</sup> <sup>−</sup>169.3 (2F), <sup>−</sup>71.7 (12F) ppm; MS (MALDI-TOF): *<sup>m</sup>*/*<sup>z</sup>* = 1429 (M<sup>+</sup> ).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-heptafluoropropane-2-sulfonylcarbamoyl-methoxy)calix[4]arene-propylenecrown-6 22.** Under Ar, compound **16b** (41 mg, 42 µmol), 6-chloro-1-hydroxybenzotriazole (16 mg, 92 µmol), EDC · HCl (18 mg, 92 µmol), and Et3N (13 µL, 9.3 mg, 92 µmol) was dissolved in anhydrous acetonitrile (8 mL) and stirred at 0 ◦C for 30 min. Afterwards, heptafluoroisopropane-2-sulfonamide (42 mg, 167 µmol) and Et3N (12 µL, 8.4 mg, 84 µmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (15 mL) and the organic phase was washed with brine (15 mL), saturated hydrogen carbonate solution (15 mL) and brine (15 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified using column chromatography (petroleum ether:ethyl acetate = 4:1 → 2:1) to obtain **22** as colourless solid (24 mg, 40%); mp >350 ◦C; R*<sup>f</sup>* = 0.6 (petroleum ether:ethyl acetate = 2:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.07 (s, 18H, <sup>t</sup>Bu), 1.18 (s, 18H, <sup>t</sup>Bu), 2.09–2.01 (m, 2H, CH2), 3.36 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, CH2Ar), 3.74–3.69 (m, 4H, OCH2), 3.82–3.74 (m, 8H, 2 × OCH2), 3.89–3.82 (m, 4H, OCH2), 4.07–4.00 (m, 4H, OCH2), 4.16 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, CH2Ar), 4.58 (s, 4H, CH2C=O), 7.04 (s, 4H, ArH), 7.13 (s, 4H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.0 (CH2Ar), 30.3 (CH2), 31.3 (CH3), 31.5 (CH3), 34.2 (Cq), 34.3 (Cq), 70.4 (OCH2), 71.1 (OCH2), 71.4 (OCH2), 72.5 (OCH2), 77.4 (CH2C=O), 78.0 (OCH2), 125.9 (CHAr), 126.5 (CHAr), 134.1, 134.5, 147.7, 148.4, 148.8, 151.0 (6 × CAr), 175.9 (C=O); <sup>19</sup>F NMR (376 MHz, CDCl3): <sup>δ</sup> <sup>−</sup>169.5 (hept, <sup>3</sup> *<sup>J</sup>* = 7.5 Hz, 2F), <sup>−</sup>71.7 (d, <sup>3</sup> *J* = 7.5 Hz, 12F) ppm; MS (ESI+): *m*/*z* = 1466 (M<sup>+</sup> + Na).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-trifluormethanesulfonylcarbamoylmethoxy)-calix[4]arene-benzocrown-6 23.** Under Ar, compound **16c** (100 mg, 99 µmol), 6-chloro-1-hydroxybenzotriazole (37 mg, 0.22 mmol), EDC · HCl (42 mg, 0.22 mmol), and Et3N (30 µL, 22 mg, 0.22 mmol) were dissolved in anhydrous acetonitrile (10 mL) and stirred at 0 ◦C for 30 min. Afterwards, trifluoromethanesulfonamide (59 mg, 0.39 mmol) and Et3N (27 µL, 20 mg, 0.20 mmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (15 mL) and the organic phase was washed with water (15 mL), saturated hydrogen carbonate solution (15 mL) and water (15 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified using column chromatography (petroleum ether:ethyl acetate = 2:1 → 3:2) to obtain **23** as yellowish solid (122 mg, 97%); mp 320 ◦C (decomp.); R*<sup>f</sup>* 0.6 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.13 (s, 18H, <sup>t</sup>Bu), 1.15 (s, 18H, <sup>t</sup>Bu), 1.10–1.16 (m, 36H, CH3), 3.40 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, CH2Ar), 3.96–4.02 (m, 4H, OCH2), 4.04–4.21 (m, 12H, OCH2, CH2Ar), 4.27–4.33 (m, 4H, OCH2), 4.64 (s, 4H,

CH2C=O), 6.88–6.98 (m, 4H, ArH), 7.07–7.14 (m, 8H, ArH) ppm; <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.3 (CH2Ar), 31.3 (CH3), 31.4 (CH3), 34.2 (Cq), 34.3 (Cq), 67.0 (OCH2), 70.6 (OCH2), 72.6 (OCH2), 77.4 (CH2C=O), 78.3 (OCH2), 111.7 (CHAr), 121.6 (CHAr), 125.8 (CHAr), 126.3 (CHAr), 134.2, 134.3, 147.0, 148.0, 148.1, 148.4, 151.6 (7 × CAr), 176.3 (C=O); <sup>19</sup>F NMR (376 MHz, CDCl3): <sup>δ</sup> <sup>−</sup> 76.6 (CF3) ppm; MS (ESI+): *<sup>m</sup>*/*<sup>z</sup>* = 1278 (M<sup>+</sup> + H), 1295 (M<sup>+</sup> + NH4), 1295 (M<sup>+</sup> + Na).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-heptafluoropropane-2-sulfonylcarbamoyl-methoxy)calix[4]arene-benzocrown-6 24.** Under Ar, compound **16c** (67 mg, 66 µmol), 6-chloro-1-hydroxybenzotriazole (20 mg, 0.15 mmol), EDC · HCl (29 mg, 0.15 mmol), and Et3N (21 µL, 15 mg, 0.15 mmol) were dissolved in anhydrous acetonitrile (10 mL) and stirred at 0 ◦C for 30 min. Afterwards, heptafluoroisopropane-2-sulfonamide (66 mg, 0.26 mmol) and Et3N (18 µL, 13 mg, 0.13 mmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (15 mL) and the organic phase was washed with water (15 mL), saturated hydrogen carbonate solution (15 mL) and water (15 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified using column chromatography (DCM → DCM:methanol = 74:1) to obtain **24** as colorless solid (50 mg, 50%); mp 340 ◦C (decomp.); R*<sup>f</sup>* 0.7 (DCM:methanol = 98:2); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.10 (s, 18H, <sup>t</sup>Bu), 1.17 (s, 18H, <sup>t</sup>Bu), 3.41 (d, <sup>2</sup> *J* = 12.4 Hz, 4H, CH2Ar), 3.98–4.06 (m, 8H, OCH2), 4.17 (d, 2 *J* = 12.4 Hz, 4H, CH2Ar), 4.20–4.25 (m, 8H, OCH2), 4.65 (s, 4H, CH2C=O), 6.84–6.88 (m, 2H, ArH), 6.93–6.97 (m, 2H, ArH), 7.06 (s, 4H, ArHCalix), 7.14 (s, 4H, ArHCalix); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 30.3 (CH2Ar), 31.4 (CH3), 31.4 (CH3), 34.2 (Cq), 34.3 (Cq), 66.5 (OCH2), 70.2 (OCH2), 72.8 (CH2C=O), 76.8 (OCH2), 78.1 (OCH2), 110.9 (CHAr), 119.0 (dd, <sup>1</sup> *J*C-F = 288 Hz, 3 *J*C-F = 26 Hz, CF), 119.5 (qd, <sup>1</sup> *J*C-F = 288 Hz, <sup>3</sup> *J*C-F = 26 Hz, CF3), 121.4 (CHAr), 125.8 (CHAr), 126.3 (CHAr), 134.1, 134.2, 146.8, 147.9, 148.0, 148.5, 151.9 (7 × CAr), 176.1 (C=O); <sup>19</sup>F NMR (564 MHz, CDCl3): <sup>δ</sup> <sup>−</sup> 72.0 (d, <sup>3</sup> *<sup>J</sup>* = 7.0 Hz), <sup>−</sup>169.9 (hept, <sup>3</sup> *J* = 7.0 Hz) ppm; MS (MALDI-TOF): *m*/*z* = 1499 (M<sup>+</sup> + Na).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-pentafluorobenzenesulfonylcarbamoylmethoxy)-calix[4]arene-benzocrown-6 25**. Under Ar, compound **16c** (100 mg, 99 µmol), 6-chloro-1-hydroxybenzotriazole (37 mg, 0.22 mmol), EDC · HCl (42 mg, 0.22 mmol), and Et3N (30 µL, 22 mg, 0.22 mmol) were dissolved in anhydrous acetonitrile (10 mL) and stirred at 0 ◦C for 30 min. Afterwards, pentafluorobenzenesulfonamide (97 mg, 0.39 mmol) and Et3N (27 µL, 20 mg, 0.20 mmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (15 mL) and the organic phase was washed with water (15 mL), saturated hydrogen carbonate solution (15 mL) and water (15 mL), dried over Na2SO<sup>4</sup> and the solvent was removed. The crude product was purified using column chromatography (petroleum ether:ethyl acetate = 2:1 → 3:2), dissolved again in DCM and washed with 10% HCl to obtain **25** as yellowish solid (122 mg, 97%); mp 320 ◦C (decomp.); R*<sup>f</sup>* 0.6 (petroleum ether:ethyl acetate = 1:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.83 (s, 18H, CH3), 1.24 (s, 18H, CH3), 3.14 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 4.00–4.10 (m, 8H, OCH2), 4.17–4.23 (m, 4H, OCH2), 4.32 (d, <sup>2</sup> *J* = 12.8 Hz, 4H, ArCH2), 4.41–4.47 (m, 4H, OCH2), 5.17 (s, 4H, OCH2CO), 6.47 (s, 4H, ArH), 6.93 (s, 4H, ArH), 6.96–7.02 (m, 4H, ArH), 11.12 (s, 2H, C=O); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 31.1 (CH3), 31.6 (CH3), 32.1 (ArCH2), 33.8 (Cq), 34.2 (Cq), 68.1 (OCH2), 70.0 (OCH2), 70.3 (OCH2C=O), 71.7 (OCH2), 73.4 (OCH2), 114.0 (CHAr), 122.1 (CHAr), 125.0 (CHAr), 125.4 (CHAr), 131.9, 135.1, 145.4, 146.1, 148.0, 151.4, 152.5 (7 × CAr), 168.8 (C=O); <sup>19</sup>F NMR (376 MHz, CDCl3): <sup>δ</sup> <sup>−</sup>138.6 (d, <sup>3</sup> *<sup>J</sup>* = 20.4 Hz), <sup>−</sup>148.6 (d, <sup>3</sup> *J* = 20.4 Hz), <sup>−</sup>163.5 (t, <sup>3</sup> *J* = 20.4 Hz) ppm; MS (ESI +): *m*/*z* = 1474 (M<sup>+</sup> + H), 1491 (M<sup>+</sup> + NH4), 1518 (M<sup>+</sup> <sup>−</sup> H + 2 Na), 1534 (M<sup>+</sup> <sup>−</sup> H + Na + K).

**Disodium 5**,**11**,**17**,**23-tetrakis(***tert***-butyl)-25**,**27-bis(***N***-heptafluoro-2-propanesulfonylcarbamoyl-methoxy)calix[4]arene-4-***tert***-butylcarboxybenzocrown-6 26**. Under Ar, compound **16e** (26 mg, 42 µmol), 6-chloro-1-hydroxybenzotriazole (9 mg, 51 µmol), EDC · HCl (10 mg, 51 µmol), and Et3N (7,1 µL, 5 mg, 51 µmol) were dissolved in anhydrous acetonitrile (8 mL) and stirred at 0 ◦C for 30 min. Afterwards, heptafluoropropane-2-sulfonamide

(23 mg, 0.093 mmol) and Et3N (6.5 µL, 5 mg, 0.084 mmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (15 mL) and the organic phase was washed with water (15 mL), saturated hydrogen carbonate solution (15 mL) and water (15 mL), dried over Na2SO<sup>4</sup> and the solvent removed. The crude product was purified using column chromatography (petroleum ether:ethyl acetate 3:1 → 2:1) to obtain **26** as colourless solid (13 mg, 35%); mp 340 ◦C (decomp.); R*<sup>f</sup>* 0.3 (petroleum ether:ethyl acetate 2:1); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 1.10 (s, 18H, CH3), 1.17 (s, 18H, CH3), 1.61 (s, 9H, OC(CH3)3), 3.41 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, ArCH2), 3.98–4.10 (m, 8H, OCH2), 4.16 (d, <sup>2</sup> *J* = 12.3 Hz, 4H, ArCH2), 4.21–4.31 (m, 8H, OCH2), 4.64 (s, 4H, OCH2CO), 6.86 (d, <sup>3</sup> *J* = 8.5 Hz, 1H, ArH), 7.06 (s, 4H, ArH), 7.14 (s, 4H, ArH), 7.50 (d, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH), 7.67 ppm (dd, <sup>3</sup> *J* = 8.5 Hz, <sup>4</sup> *J* = 1.9 Hz, 1H, ArH); <sup>13</sup>C NMR (101 MHz, CDCl3): δ 28.4 (OtBu), 30.3 (ArCH2), 30.4 (ArCH2), 31.3 (tBu), 31.4 (tBu), 34.2 (Cq), 34.3 (Cq), 66.9 (OCH2), 67.2 (OCH2), 69.9 (OCH2), 70.0 (OCH2), 72.8 (OCH2), 72.9 (OCH2), 76.7 (OCH2CO), 78.0 (OCH2), 78.1 (OCH2), 80.9 (OCq), 110.2 (CHAr), 111.8 (CHAr), 124.0 (CHAr), 125.4 (CAr), 125.8 (CHAr), 126.3 (CHAr), 134.1, 134.2, 146.4, 147.9, 148.0, 148.1, 148.5, 150.3, 151.8, 151.9 (10 <sup>×</sup> <sup>C</sup>Ar), 165.6 (C=OOtBu), 176.1 (C=ONH); <sup>19</sup><sup>F</sup> NMR (376 MHz, CDCl3): <sup>δ</sup> <sup>−</sup>72.0 (m, 6F), <sup>−</sup>169.9 (hept, <sup>3</sup> *J* = 7.3 Hz, 1F) ppm; MS (ESI +): *<sup>m</sup>*/*<sup>z</sup>* = 1595 (M<sup>+</sup> + NH4), 1600 (M<sup>+</sup> + Na), 1616 (M<sup>+</sup> + K), 1622 (M<sup>+</sup> <sup>−</sup> H + 2 Na).

**5**,**11**,**17**,**23-Tetrakis(***tert***-butyl)-25**,**27-bis(***N***-heptafluoro-2-propanesulfonylcarbamoyl-methoxy)calix[4]arene-benzocrown-8 27.** Under Ar, compound **16d** (135 mg, 0.12 mmol), 1-hydroxybenzotriazole (36 mg, 0.27 mmol), EDC · HCl (52 mg, 0.27 mmol), and Et3N (37 µL, 27 mg, 0.27 mmol) were dissolved in anhydrous acetonitrile (20 mL) and stirred at 0 ◦C for 30 min. Afterwards, heptafluoropropane-2-sulfonamide (122 mg, 0.49 mmol) and Et3N (34 µL, 25 mg, 0.24 mmol) dissolved in anhydrous acetonitrile (5 mL) were added and the resulting mixture stirred at rt overnight. Next, the solvent was changed to DCM (20 mL) and the organic phase was washed with water (20 mL), saturated hydrogen carbonate solution (20 mL) and water (20 mL), dried over Na2SO<sup>4</sup> and the solvent removed. The crude product was purified using column chromatography (DCM:petroleum ether:ethyl acetate 3:8:2 → DCM:ethyl acetate 1:1) and washed with 10% aqueous HCl to obtain **27** as colourless solid (51 mg, 27%); mp 162 ◦C; R*<sup>f</sup>* 0.25 (DCM:petroleum ether:ethyl acetate 3:8:2); <sup>1</sup>H NMR (400 MHz, CDCl3): δ 0.82 (s, 18H, CH3), 1.31 (s, 18H, CH3), 3.22 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, ArCH2), 3.77–3.79 (m, 4H, OCH2), 3.79–3.82 (m, 8H, OCH2), 3.98–4.00 (m, 4H, OCH2), 4.07–4.10 (m, 4H, OCH2), 4.20–4.23 (m, 4H, OCH2), 4.55 (d, <sup>2</sup> *J* = 13.0 Hz, 4H, ArCH2), 5.28 (s, 4H, OCH2CO), 6.50 (s, 4H, ArH), 6.84–6.89 (m, 2H, ArH), 6.90–6.95 (m, 2H, ArH), 7.08 (s, 4H, ArH); <sup>13</sup>C NMR (151 MHz, CDCl3): δ 33.7 (tBu), 34.2 (tBu), 34.7 (ArCH2), 36.2 (Cq), 36.7 (Cq), 69.4 (OCH2), 71.5 (OCH2), 71.9 (OCH2), 72.9 (OCH2), 73.3 (OCH2CO), 73.4 (OCH2), 114.5 (CHAr), 123.7 (CHAr), 127.5 (CHAr), 128.4 (CHAr), 134.7, 137.8, 147.7, 148.1, 150.4, 154.0 (6 <sup>×</sup> <sup>C</sup>Ar); <sup>19</sup>F NMR (564 MHz, CDCl3): <sup>δ</sup> <sup>−</sup>71.7 (d, <sup>3</sup> *J* = 8.0 Hz, 6F), −168.5 (m, 1F) ppm; MS (ESI +): *<sup>m</sup>*/*<sup>z</sup>* = 1394 (M<sup>+</sup> <sup>−</sup> <sup>H</sup> <sup>−</sup> NHSO2CF(CF3)<sup>2</sup> + K + Na), 1625 (M<sup>+</sup> <sup>−</sup> H + K + Na).
