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, After the last addition, the mixture was stirred for another 2h in the dark at the same temperature. The resulting mixture was filtered hot, the red residue was redissolved in 2M sodium hydroxide (200 mL), sodium metabisulfite (10 g) was added and the clear orange solution was acidified with conc HCl until pH<1

, Purification by recrystallization (acetic acid, 100 mL) afforded II-23 as shiny red crystals (1.62 g, 30% yield)

H. Nmr, DMSO-d6) ? 12, 300 MHz

, Analysis is in agreement with literature data, Organometallics, vol.5899, p.32, 2013.

, Dimethyl 5-hydroxyisophthalate II-45

. -hydroxyisophthalic-acid, 11 g, 50 mmol) was suspended in methanol (300 mL) at room temperature, then sulfuric acid (0.2 mL) was added and stirred at reflux overnight. After cooling to room temperature, the pale yellow solution was poured into ice H 2 O (900 mL) and stirred vigorously for 1 hour. The white precipitate was filtered and

, Purification by recrystallization (methanol, 200 mL) afforded II-45 as white cotton-like crystals (10.5 g, quantitative yield)

H. Nmr, 300 MHz

, Analysis is in agreement with literature data, J. Am. Chem. Soc, vol.335, p.139, 2017.

, 13 mL, 100 mmol) were dissolved in EtOH (200 mL), then 2M sodium hydroxide solution (200 mmol) was added. The reaction mixture was stirred at room temperature overnight, then it was diluted in distilled water (2 L) and concentrated hydrochloric acid until pH=0, where precipitation of a pale fluffy solid occurred. The heterogeneous mixture was stirred for 1 hour, then the crude was recovered by filtration and washed with distilled water (500 mL), Hydroxyacetophenone III-23 (13.6 g, 100 mmol) and benzaldehyde, p.200

H. Nmr, 300 MHz, acetone-d 6 ): ? = 7.99?8.04 (m, 2H), 7.77?7.84 (m, 1H), 7.60?7.68

, Analysis is in agreement with literature data, vol.4576, p.140, 2015.

, then diethylamine (23 mL, 223 mmol) and nitromethane (24 mL, 447 mmol) were added and the reaction mixture was stirred at reflux overnight. The reaction mixture was cooled at room temperature and concentrated under reduced pressure. The residue was partitioned between 4M HCl (100 mL) and AcOEt (100mL), the organic layer was separated, washed with brine (100 mL), dried over Na 2 SO 4 and the solvent was removed under reduced pressure, Hydroxychalcone III-24 (10 g, 44.6 mmol) was suspended in EtOH (70 mL)

H. Nmr, 300 MHz, CDCl 3 ): ? 7.86 (d, J = 8.5 Hz, 2H), vol.7, pp.35-42

, Analysis is in agreement with literature data, Org. Lett, issue.5386, p.11, 2009.

, g, 3.1 mmol) and N,N-diisopropylethylamine (5.4 mL, 31 mmol) were dissolved in DCM (150 mL), then boron trifluoride etherate complex (5.5 mL, 43.5 mmol) was added. The solution was stirred at room temperature overnight, then the mixture was diluted with AcOEt (300 mL) and washed with brine (300 mL). The organic phase was dried over Na 2 SO 4 and the solvent was removed

, BF 2 Chelate of 4-{4-phenyl-5-[3-phenyl-5-(4-prop-2-ynyloxyphenyl)-pyrrol-2-ylideneamino

, g, 2 mmol) and caesium fluoride (53 mg, 2.2 mmol) were dissolved in DMSO (25 mL), then propargyl bromide (80% wt in PhMe, 0.4 mL, 2.2 mmol) was added. The solution was stirred at 40 °C for 30 minutes, then the mixture was cooled in an ice bath to 0°C, a saturated solution of NH 4 Cl (30 mL) was added and the product extracted with ethyl acetate (2 × 30 mL). The combined organic layers were washed with brine

, Na 2 SO 4 , filtered and concentrated under reduced pressure. Purification by column chromatography (SiO 2 , DCM 100% to DCM/ethyl acetate 9:1, v/v) afforded III-28 as a red metallic solid (1.58 g, 90% yield)

H. Nmr, 300 MHz, CDCl 3 ) ? 8.18 -7.99 (m, 8H), 7.56 -7.41 (m, 6H), vol.7

, Analysis is in agreement with literature data, Org. Lett, vol.11, pp.5386-5389, 2009.

, mg, 0.2 mmol) and potassium carbonate (138 mg, 1 mmol) were dissolved in acetone (10 mL), then tert-butylbromoacetate (0.05 mL, 0.3 mmol). The solution was stirred at reflux overnight, then the mixture was cooled, the solvent was removed and the crude was redissolved in DCM (25 mL). The organic layer was washed with water (50 mL) and brine (50 mL), dried over Na 2 SO 4 , filtered the solvent removed

H. Nmr, 600 MHz, CDCl 3 ) ? 8.17 -8.04 (m, 8H), 7.52 -7.39 (m, 6H), vol.7

C. Nmr, MHz, issue.151

, HRMS (ESI) calcd for C 41 H 34 BN 3 O 4 F 2 Na, vol.9

, N-dimethylaniline) III-36 (4.12 g 10 mmol) was dissolved in dry THF (100 ml) and stirred at -80 °C. sec-BuLi (1.3 M solution in cyclohexane, p.20

, 26 mmol) was slowly added for 30 min to the solution and stirred for further 15 min at the same temperature. Dichlorodimethylsilane (1.8 mL, 15 mmol) was added to the reaction mixture and stirred at room temperature overnight. 1M HCl aqueous solution (100 mL) was added carefully to neutralize the solution, and solvent was evaporated. The resulting aqueous solution was extracted with ethyl acetate (3 ? 50 mL), and the organic phase was washed with saturated aqueous sodium bicarbonate solution (100 mL), water (100 mL) and brine (100 mL), dried over Na 2 SO 4 , filtered and the solvent removed. The crude III-37 was dissolved in degassed acetone (30 mL) at 0 °C, then KMnO 4 powder (9.48 g, 60 mmol) was added portionwise over 1 hour, and 4 , filtered and the solvent removed. Purification by column chromatography

H. Nmr, CDCl 3 ) ? 8.44 (d, 2H, J = 8.9 Hz), MHz, vol.6, issue.300

, Analysis is in agreement with literature data, Nat. Chem, 2013.

, After cooling to room temperature and evaporation of the solvent, the residue was redissolved in diethyl ether (50 ml) and washed with saturated aqueous sodium bicarbonate solution (50 mL), water (50 mL) and brine (50 mL). The organic layer was dried over Na 2 SO 4

, SiO 2 , petroleum ether/ethyl acetate 95:5, v/v) afforded III-40 as a colourless oil

H. Nmr, CDCl 3 ) ? 8.44 (d, 2H, J = 8.9 Hz), MHz, vol.6, issue.300

, Analysis is in agreement with literature data, Nat. Chem, vol.132, issue.5, 2013.

, Carboxyl-methyl silicon rhodamine III-34

, Ester III-40 (542 mg, 2 mmol) was dissolved in dry THF (10 ml) and cooled at -80 °C

, 2 mL, 3.8 mmol) was slowly added dropwise and the solution was stirred at the same temperature for 15 min. Ketone III-38 (162 mg, 0.5 mmol) in dry THF

, The organic layer was dried over MgSO 4 , filtered and the solvent removed

, then 6M aqueous hydrochloric acid (50 ml) was added and stirred at 50 °C for 3 hours. After cooling to room temperature, the solution was poured into 0.1 M aqueous sodium hydroxide solution, Crude III-41 was dissolved in MeCN (15 ml)

, The organic layer was dried over MgSO 4 , filtered and the solvent removed. Purification by column chromatography (DCM/MeOH 9:1, v/v) afforded III-34 as a blue solid (177 g, 80% yield over two steps)

H. Nmr, 300 MHz, MeOD-d 4 ) ? 8.12 (d, J = 7.3 Hz, 1H), 7.77 (s, 1H), 7.49 (d, J = 7.6 Hz, 1H), 7.39 (s, 2H), 7.07 (d, J = 9

, Analysis is in agreement with literature data, Nat. Chem, vol.132, issue.5, 2013.

, g, 30 mmol) and freshly recrystallized phenol (56.4 g, 600 mmol) were charged in a 250 mL flask. The mixture was stirred at 180 °C overnight, then toluene (200 mL) was added while cooling and washed with a 2M aqueous sodium hydroxide solution (3 ? 100 mL) and brine (2 ? 100 mL). The organic phase was dried over Na 2 SO 4 and the solvent was removed. Purification by boiling the crude residue in n-hexane (500 mL) afforded 4

H. Nmr, 7.19 (d, J = 8.5 Hz, 6H), 7.1 (d, J = 8.6 Hz, 6H), 6.84 (d, J = 8.9 Hz, 2H), 1.35 (s, 27H) Analysis is in agreement with literature data, 300 MHz, CDCl 3 ) ? 7.31 (d, J = 8.5 Hz, 6H), vol.3748, p.58, 1993.

, 200 mmol) were dissolved in DCM (200 mL), then tosyl chloride (20.9 g, 110 mmol) was added. The reaction mixture was stirred at room temperature overnight, the crude was isolated upon quenched with water (200 mL), followed by extraction with DCM (4 ? 100 mL). The organic layer was separated and dried over, Azidopropanol III-47 (10.1 g, 100 mmol) and Et 3 N (27.8 mL

, SiO 2 , petroleum ether/DCM 9:1, v/v) afforded 3-azidopropyl-4-methylbenzenesulfonate III-48 as a slightly yellow oil

H. Nmr, MHz, issue.300

. Hz,

, Analysis is in agreement with literature data, Org. Lett, p.16, 1358.

, Azide trityl stopper III-50

, g, 10 mmol) was dissolved in acetone (50 mL), then anhydrous potassium carbonate (2.76 g, 20 mmol) and 1-azido-3-iodopropane, p.12

, The suspension was stirred at reflux overnight, then the solvent was removed, water (100 mL) was added and extracted with DCM (4 ? 50 mL). The organic phase was dried over

, Na 2 SO 4 and the solvent was removed. Purification by column chromatography

H. Nmr, MHz CDCl 3 ): ? 7.30 (d, J = 8.6 Hz, 6H)

. Hz, , vol.2

. Hz,

, 1.30 (s, 27H)

, Analysis is in agreement with literature data, J. Am. Chem. Soc, vol.128, 2006.

, Alkyne trityl stopper II-14

, 10 mmol) was dissolved in acetone (50 mL), then anhydrous potassium carbonate (2.76 g, 20 mmol) and propargyl bromide (80% wt in PhMe, 12 mmol) were added. The suspension was stirred at reflux overnight, then the solvent was removed, water (100 mL) was added and extracted with DCM (4 ? 50 mL). The organic phase was dried over Na 2 SO 4 and the solvent was removed. Purification by recrystallization

H. Nmr, MHz CDCl, vol.3, issue.300

. Hz,

, Analysis is in agreement with literature data, J. Am. Chem. Soc, 2006.

, -azido-propanyl) barbituric acid II-12, p.5

, 80 mmol) was suspended in DMSO (50 mL) at room temperature, then urea (12 g, 200 mmol) was slowly added. The mixture was stirred at the same temperature for 1 hour

H. Nmr, 300 MHz): ? 8

, Analysis is in agreement with literature data, Org. Lett, p.16, 1358.

, Tetrakis(acetonitrile)copper(I) hexafluorophosphate

, 113 mmol) was added dropwise to a suspension of copper(I) oxide (4 g, 28 mmol) in acetonitrile (80 mL) at room temperature. The solution was stirred for 5 minutes at room temperature, vol.10

, The white precipitate was filtered, washed with Et 2 O (100 mL) and redissolved in MeCN (100 mL). The pale blue solution was refluxed for 5 minutes, cooled at room temperature then Et 2 O (100 mL) was added and the resulting mixture was cooled at -20 °C overnight, through Celite and the filtrate was cooled at -20 °C overnight

, hexafluorophosphate was recovered by filtration as white crystalline powder (10 g, 96% yield)

. Elem,

, P, vol.8, issue.1

, Analysis is in agreement with literature data (Inorganic Syntheses, vol.19, 1979.

, Barbiturate-containing BF 2 -chelate azadipyrromethene thread III-52

, 1 mmol) and BF 2 -chelate monopropargylated azadipyrromethene III-28 (124 mg, 0.22 mmol) were dissolved in a dry degassed 1:1, v/v, chloroform/methanol mixture (2 mL) and stirred at room temperature for 1 hour. Tetrakis(acetonitrile)copper(I) hexafluorophosphate (82 mg, 0.22 mmol) and DIPEA (0.07 mL, 0.44 mmol) were then added and the reaction mixture 4 , filtered and the solvent was removed

H. Nmr, 300 MHz, CD 2 Cl 2 ) ? 8.14 -7.98 (m, 16H), 7.74 (s, 2H), 7.52 -7.36 (m, 12H), vol.7

T. Glaser,

. Macrocycle, mg, 0.1 mmol) and copper (I) iodide (19 mg, 0.1 mmol) were dissolved in 1:1, v/v dichloromethane/acetonitrile mixture (1 mL) and stirred at room temperature for 1 hour

, 1 mmol) and alkyne stopper II-14 (109 mg, 0.2 mmol) were added and the reaction mixture was stirred at 60 °C for 72 hours. Then the reaction mixture was cooled to room temperature and the solvent was removed. The crude was redissolved in DCM (5 mL) and the organic layer was washed with 1M aqueous solution of potassium cyanide (5 mL), water (5 mL) and brine (5 mL). The solution was dried over MgSO 4 , filtered and the solvent removed, Iodine (253 mg, 1 mmol), potassium carbonate (138 mg

J. , Hz, 2H), 7.67 (t, J = 8.1 Hz, 2H), 7.51 (s, 1H), 7.31 (s, 2H), 7.22 -7.18 (m, 8H), 7.16 -7.13 (m, 3H), 7.03 -6.99 (m, 8H)

C. Nmr, MHz, issue.151

, HRMS (FD) calcd for C 128 H 145 N 7 O 8 [M] + m/z = 1908.1154

, 10 mmol) was dissolved in DCM (100 mL), then dibutylamine (5.2 g, 40 mmol) was added. The reaction mixture was stirred overnight then it was quenched upon sequential addition of 1M sodium hydroxide solution (100 mL), 1M hydrochloric acid solution (100 mL), water (100 mL) and brine (100 mL). The organic layer was dried over MgSO 4 , filtered and the solvent removed

H. Nmr, 300 MHz): ? 3.25-3.18 (m, 8H), 2.61 (s, 4H), vol.1

, Analysis is in agreement with literature data, J. Org. Chem, p.80, 2015.

1. Hz,

C. Nmr, MHz, vol.87, issue.151

, HRMS (ESI) calcd for C 80 H 94 N 8 O 10 Na [M+Na] + m/z = 1349.6985, found m/z = 1349.6928. 2.70 (m, 4H), 1.59 -1.49 (m, 8H), vol.1

C. Nmr, MHz, issue.151

, HRMS (FD) calcd for C 72 H 84 N 6 O 4 NFe

, 54 mmol) was dissolved in conc. H 2 SO 4 (150 mL), and stirred for 6 h, Ferrocene II-17 (10 g

, A solution of NaNO 2 (5 g, 72.5 mmol) in H 2 O (10 mL) was then added dropwise at 0°C. This solution was then stirred at 0°C for 1 h, and then used immediately. The ferrocenium sulfate solution was added to ice H 2 O (600 mL) and allowed to warm to room temperature. Copper powder (5 g, 78.5 mmol) was then added. This mixture was poured onto the diazonium ion solution, with the reaction mixture being stirred at 0°C for 30 min, then allowed to warm to room temperature and stirred for 24 hours. Excess ascorbic acid (30 g) was then added, followed by DCM (1 L). This mixture was filtered through Celite and washed thoroughly with DCM. The organic layer was washed with brine (5 ? 100 mL), dried over MgSO 4 and the solvent removed, Meanwhile, dimethyl 5-aminoisophthalate II-40 (3.7 g, 17.5 mmol) was suspended in conc. HCl (50 mL) and H 2 O (50 mL), and cooled to 0°C

H. Nmr, CDCl 3 ) ? 8.46 (t, J = 1.6 Hz, 1H), MHz, vol.8, issue.300

, Analysis is in agreement with literature data, Chem. Sci, 1080.

, 13 mmol) and water (10 mL) were added. The reaction mixture was stirred at reflux overnight, then cooled and the solvent removed. The crude was redissolved in water (100 mL) and 10% aqueous citric acid was added until precipitation occurred. The resulting orange precipitate was collected by filtration and washed with water (50 mL), Dimethyl 5-ferrocenylisophthalate IV-27 (980 mg, 2.6 mmol) was suspended in EtOH (100 mL), then potassium hydroxide (728 mg

H. Nmr, DMSO-d 6 ) ? 8.46 (t, J = 1.6 Hz, 1H), 300 MHz, vol.8

. Hz,

, Analysis is in agreement with literature data, Chem. Sci, 1080.

, The reaction mixture was stirred at room temperature overnight. The mixture was concentrated under reduced pressure to afford IV-25 as blood red oil (804 mg, quantitative yield), -Ferrocenylisophthalic acid IV-28 (700 mg