Organic Letters. Synthesis of Oxygen-Free [2]Rotaxanes: Recognition of Diarylguanidinium Ions by Tetraazacyclophanes. and Sheng-Hsien Chiu*
|
|
- Maria Hunter
- 5 years ago
- Views:
Transcription
1 Organic Letters Synthesis of Oxygen-Free [2]Rotaxanes: Recognition of Diarylguanidinium Ions by Tetraazacyclophanes Yu-Hsuan Chang, Yong-Jay Lee, Chien-Chen Lai, Yi-Hung Liu, Shie-Ming Peng, and Sheng-Hsien Chiu* Supplementary Material Data Page Number Experimental procedures and characterization data for new compounds... S2 S10 1 H and 13 C NMR spectra of the cyclophane 1, 5, 10 and S11 S18 1 H and 13 C NMR spectra of the dibromide 6 and S19 S22 1 H and 13 C NMR spectra of the salt 9-, 16 and 22 TFPB... S23 S28 1 H and 13 C NMR spectra of the compound S1-S5... S29 S38 1 H and 13 C NMR spectra of the [2]rotaxane (18-21) TFPB... S39 S46 1 H and 13 C NMR spectra of the [2]rotaxane 23 TFPB and 24 TFPB... S47 S50 ITC titration isotherms and thermodynamic data for the complexation of 9 TFPB with the cyclophanes in CHCl 3... S51 S56 Dilution isotherm for the cyclophanes and 9 TFPB in CDCl3... S57 S58 Competition experiment of the cyclophane 1 and 5 with 9 TFPB in CDCl 3... S59 Competition experiment of the cyclophane 10 and 13 with 9 TFPB in CDCl 3... S60 1 H NMR spectra for assembly of [2]rotaxanes from 16 TFPB, cyclophane 1, and aldehyde S61 NOESY spectra for the equimolar mixtures of 9 TFPB and the cyclophanes (20 mm)... S62 S65 ESI-MS spectra of the [2]rotaxane TFPB and TFPB... S66 S71 S1
2 General All glassware, stirrer bars, syringes, and needles were either oven- or heat gun-dried prior to use. All reagents were obtained from commercial sources unless otherwise indicated. Reactions were conducted under Ar or N 2 atmospheres. Thin layer chromatography (TLC) was performed on Merck 0.25 mm silica gel (Merck Art. 5715). Column chromatography was performed using Kieselgel 60 (Merck, mesh) and Chromatorex NH series / DIOL series (Fuji Silysia, MB100-40/75). Melting points were determined by Fargo MP-2D melting point apparatus. For NMR spectroscopy, the deuterated solvent was used as the lock, and the solvent s residual protons were employed as the internal standard. Cyclophane 1: A CHCl 3 solution mixture (149 ml) of 1,3-phenylenedimethanamine (3) (406 mg, 395 μl, 2.98 mmol) and isophthalaldehyde (2) (400 mg, 2.98 mmol) was stirred at 50 C for 48 h and slowly added to a MeOH solution (298 ml) of NaBH 4 (4.51 g, 119 mmol). The organic solvents were evaporated under reduced pressure and the residue was partitioned between H 2 O (150 ml) and CH 2 Cl 2 (2 150 ml). The combined organic phases were dried (MgSO 4 ), concentrated and purified chromatographically (NH-silica gel; CH 2 Cl 2 /hexanes, 1:1) to afford cyclophane 1 as a white solid (432 mg, 61%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 3.78 (s, 16H), 7.19 (d, J = 8.0 Hz, 8H), (m, 10H); 13 C NMR (100 MHz, CDCl 3 ): δ = 53.6, 127.1, 127.8, 128.4, 140.3; HR-MS (ESI): calcd for [1 + Na] + C 32 H 36 N 4 Na + : m/z ; found Dibromide 6: NaH (60%; 1.45 g, 36.3 mmol) was added to a THF solution (72.4 ml) of 1,3-benzenedimethanol (8) (1 g, 7.24 mmol) and the solution mixture was stirred at room temperature for 30 min. The solution mixture was then added 1,3-bis(bromomethyl)benzene (7.64 g, 28.9 mmol) and heated to reflux for 16 h. After cooled to room temperature, the solution mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was purified chromatographically (SiO 2 ; EtOAc/hexanes, 1:9) to afford dibromide 6 as a light brown oil (1.47 g, 40%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 4.48 (s, 4H), 4.54 (s, 4H), 4.56 (s, 4H), (m, 8H), (m, 4H); 13 C NMR (100 MHz, CDCl 3 ): δ = 33.4, 71.8, 72.3, 127.2, 127.8, 128.3, 128.3, 128.6, 128.9, 138.0, 138.3, (one signal is missing, possibly because of signal overlap); HR-MS (ESI): calcd for [6 + Na] + C 24 H 24 Br 2 O 2 Na + : m/z ; found Cyclophane 5: A THF solution mixture (32.4 ml) of the dibromide 6 (816 mg, 1.62 mmol) and 1,3-benzenedimethanol (8) (224 mg, 1.62 mmol) was added to a S2
3 suspension of THF solution suspension (129.4 ml) of NaH (60%; 324 mg, 8.10 mmol) and the solution mixture was heated to reflux for 7 days. After cooled to room temperature, the solution mixture was filtered through Celite and the filtrate was concentrated under reduced pressure. The residue was purified chromatographically (SiO 2 ; EtOAc/hexanes, 1:9) to afford cyclophane 5 as a white solid (362 mg, 47%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 4.52 (s, 16H), (m, 16H); 13 C NMR (100 MHz, CDCl 3 ): δ = 72.1, 127.2, 127.4, 128.4, 138.4; HR-MS (ESI): calcd for [5 + Na] + C 32 H 32 NaO + 4 : m/z ; found Guanidinium Salt 9 TFPB: HCl (aq) (3N, 297 μl) was added to a CH 3 CN solution (17.8 ml) of 1,3-di-p-tolylguanidine [a] (213 mg, mmol) and the solution mixture was stirred at room temperature for 10 min before the addition of NaTFPB (789 mg, mmol). The solution mixture was stirred at room temperature for 10 min and the organic solvent was removed under reduced pressure. The residue was partitioned between DI water (30 ml) and CH 2 Cl 2 (2 30 ml) and the combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (SiO 2 gel; CH 2 Cl 2 ) and the product was precipitated from hexanes to afford guanidinium salt 9 TFPB as a pale yellow solid (879 mg, 89%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 2.33 (s, 6H), 5.44 (br, 2H), 7.02 (d, J = 7.8 Hz, 4H), 7.16 (br, 2H), 7.23 (d, J = 7.8 Hz, 4H), 7.49 (s, 4H), 7.68 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ =20.9, (m), (q, 1 J CF = 271 Hz), 126.3, 127.7, (m), 131.8, 134.8, 141.7, 155.1, (q, 1 J CB = 49 Hz); HR-MS (ESI): calcd for [9] + C 15 H 18 N + 3 : m/z ; found Cyclophane 10: A CH 2 Cl 2 solution mixture (242 ml) of 1,4-phenylenedimethanamine (11) (330 mg, 2.42 mmol) and isophthalaldehyde (2) (325 mg, 2.42 mmol) was stirred at 50 C for 4 d and cooled to 0 o C before the addition of a solution mixture of MeOH/THF/toluene (200 ml/30 ml/30 ml) and NaBH 4 (3.70 g, 97.8 mmol). The solution mixture was stirred at 0 o C for 1 h and the organic solvents were removed under reduced pressure. The residue was partitioned between H 2 O (250 ml) and CH 2 Cl 2 (2 250 ml) and the combined organic layers were dried (MgSO 4 ), concentrated, and purified chromatographically (NH-silica gel; CH 2 Cl 2 /hexanes, 1:1) to afford syslophane 10 as a white solid (301 mg, 52%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 3.77 (s, 8H), 3.80 (s, 8H), (m, 4H), (m, 2H), 7.32 (s, 8H), 7.44 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 52.3, 52.5, 126.9, 127.4, 128.3, 128.4, 139.0, 140.5; HR-MS (ESI): calcd for [10 + Na] + C 32 H 36 N 4 Na + : m/z ; found S3
4 Dibromide 15: NaH (60%; 1.45 g, 36.3 mmol) was added to a THF solution (72.4 ml) of 1,3-benzenedimethanol (8) (1 g, 7.24 mmol) and the solution mixture was stirred at room temperature for 30 min. The solution mixture was then added 1,4-bis(bromomethyl)benzene (7.64 g, 28.9 mmol) and heated to reflux for 16 h. After cooled to room temperature, the mixture was filtered through Celite and the filtrate was concentrated. The residue was purified chromatographically (SiO 2 ; EtOAc/hexanes, 1:15) to afford dibromide 15 as a light brown oil (1.75 g, 48%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 4.48 (s, 4H), 4.53 (s, 4H), 4.55 (s, 4H), (m, 2H), (m, 5H), (m, 5H); 13 C NMR (100 MHz, CDCl 3 ): δ = 33.3, 71.7, 72.2, 127.0, 127.1, 128.1, 128.5, 129.1, 137.1, 138.4, 138.6; HR-MS (ESI): calcd for [15 + Na] + C 24 H 24 Br 2 NaO + 2 : m/z ; found Cyclophane 13: A THF solution (23.8 ml) of the dibromide 15 (600 mg, 1.19 mmol) and 1,3-benzenedimethanol (8) (164 mg, 1.19 mmol) was added to a THF solution suspension (95.2 ml) of NaH (60%; 240 mg, 6.00 mmol) and the solution mixture was heated to reflux for 7 days. After cooled to room temperature, the mixture was filtered through Celite and the filtrate was concentrated. The residue was purified chromatographically (SiO 2 ; EtOAc/hexanes, 1:5) to afford cyclophane 13 as a white solid (68 mg, 12%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 4.55 (s, 8H), 4.57 (s, 8H), 7.25 (d, J = 7.5 Hz, 4H), (m, 2H), 7.39 (s, 8H), 7.57 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 71.4, 71.5, 127.0, 127.0, 127.9, 128.3, 137.7, 138.6; HR-MS (ESI): calcd for [13 + Na] + C 32 H 32 NaO + 4 : m/z ; found S4
5 Thiourea S1: 1,3-di-tert-butyl-5-isothiocyanatobenzene (1.58 g, 6.39 mmol) and tert-butyl 4-aminobenzylcarbamate (945 mg, 4.25 mmol) were added to a 10 ml ball-mill jar and the solid mixture was ball-milled at room temperature for 24 h (a 30 min break was taken every 2 h to avoid overheating of the ball-miller). The solid mixture was purified chromatographically (SiO 2 ; CH 2 Cl 2 /hexanes, 2:8) to afford thiourea S1 as a brown oil (1.29 g, 65%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.30 (s, 18H), 1.43 (s, 9H), 4.28 (d, J = 4.6 Hz, 2H), 4.84 (br, 1H), 7.16 (s, 2H), 7.27 (d, J = 8.0 Hz, 2H), 7.34 (s, 1H), 7.36 (d, J = 8.0 Hz, 2H), 7.71 (s, 1H), 7.80 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ = 28.4, 31.3, 35.0, 44.1, 79.6, 119.6, 121.3, 125.1, 128.2, 136.0, 136.7, 137.4, 152.8, 155.9, ; HR-MS (ESI): calcd for [S1 + Na] + C 27 H 39 N 3 O 2 SNa + : m/z ; found Guanidine S2. A DMF solution (2.02 ml) of thiourea S1 (94.8 mg; mmol) was cooled to 0 o C and sequentially added NH 4 OH (aq) (35%; 40.4 mg, 45.9 μl, mmol), triethylamine (81.8 mg, 113 μl,0.808 mmol) and HgCl 2 (110 mg, mmol). The solution mixture was stirred virgrously at 0 o C. After the color turned black, the solution mixture was slowly warmed to room temperature and stirred for 1 h. The solution suspension was then added CH 2 Cl 2 (20 ml) and filtered through Celite. The filtrate was concentrated and the residue was partitioned between H 2 O (20 ml) and CH 2 Cl 2 (2 20 ml). The combined organic layers were dried (MgSO 4 ), concentrated, and purified chromatographically (NH-silica gel; EtOAc/hexanes, 4:6) to afford guanidine S2 as a pale yellow solid (68.1 mg, 75%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.24 (s, 18H), 1.44 (s, 9H), 4.22 (s, 2H), 4.92 (br, 1H), 5.03 (br, 2H), 6.93 (d, J = 1.5 Hz, 2H), 7.02 (d, J = 7.6 Hz, 2H),7.09 (s, 1H), 7.15 (d, J = 7.6 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 28.4, 31.4, 34.8, 44.3, 79.4, 117.7, 117.9, 123.2, 133.0, 141.3, 144.8, 150.2, 152.0, 155.9; HR-MS (ESI): calcd for [S2 + H] + C 27 H 41 N 4 O + 2 : m/z ; found Guanidine S3. A THF solution (3.92 ml) of guanidine S2 (177 mg, mmol) was added HCl (12 N, 980 μl) and stirred for 2 h. The organic solvent was removed under reduced pressure and the residue was partitioned between NaOH (aq) (10%, 40 ml) and CH 2 Cl 2 (2 40 ml). The combined organic layers were dried (MgSO 4 ), concentrated and purified chromatographically (NH-silica gel; MeOH/CH 2 Cl 2, 4:96) to afford guanidine S3 as a pale yellow solid (128 mg, 93%).; M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.22 (s, 18H), 3.72 (s, 2H), 6.92 (s, 2H), (m, 3H), 7.14 (d, J = 8.1 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.3, 34.7, 45.9, 117.6, 117.7, 123.2, 128.0, 137.5, 141.9, 143.7, 150.5, 151.7; HR-MS (ESI): calcd for [S3 + H] + C 22 H 33 N + 4 : m/z ; found S5
6 Guanidinium Salt 16 TFPB: A CH 3 CN solution (8.00 ml) of guanidine S3 (141 mg, mmol) was added HCl (aq) (3N, 133 μl) and stirred at room temperature for 10 min. The solution mixture was then added NaTFPB (354 mg, mmol) and stirred for another 10 min. The organic solvent was removed under reduced pressure and the residue was partitioned between DI water (20 ml) and CH 2 Cl 2 (2 20 ml). The combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (Diol-silica gel, MeOH/CH 2 Cl 2, 1:99) to afford guanidinium salt 16 TFPB as a pale yellow solid (444 mg, 91%); M.p. = C; 1 H NMR (400 MHz, CD 2 Cl 2 ): δ = 1.32 (s, 18H), 3.79 (s, 2H), 7.06 (d, J = 8.3 Hz, 2H), 7.12 (d, J = 1.6 Hz, 2H), 7.27 (d, J = 8.3 Hz, 2H), 7.58 (s, 4H), 7.60 (t, J = 1.6 Hz, 1H), 7.76 (t, J = 2.1 Hz, 8H); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 31.4, 35.7, 45.6, (m), 121.4, 125.2, (q, 1 J CF = 271 Hz), 127.7, (m), 130.3, 132.0, 132.0, 135.6, 143.0, 155.3, 155.9, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [16 TFPB + H] + C 54 H 46 BF 24 N + 4 : m/z ; found [2]Rotaxane 18 TFPB: 1,3-di-tert-butylbenzaldehyde (9.11 mg, 41.7 μmol) was added to a CHCl 3 solution mixture (2.09 ml) of guanidinium salt 16 TFPB (50.7 mg, 41.7 μmol) and cyclophane 1 (19.9 mg, 41.7 μmol) and the solution mixture was stirred at 50 C for 16 h. The solution mixture was then slowly added to a MeOH solution (4.17 ml) of NaBH 4 (31.6 mg, 835 μmol) and the organic solvents were removed under reduced pressure. The residue was partitioned between DI water (10 ml) and CH 2 Cl 2 (2 10 ml) and the combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (Diol-silica gel; CH 2 Cl 2 /hexanes, 1:1) to afford [2]rotaxane 18 TFPB as a colorless oil (43.6 mg, 55%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.22 (s, 18H), 1.33 (s, 18H), (m, 20H), 6.45 (d, J = 8.0 Hz, 2H), 6.76 (s, 2H), 6.91 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 7.4 Hz, 8H), 7.17 (s, 2H), (m, 4H), 7.32 (s, 4H), 7.36 (s, 1H), 7.41 (s, 1H), 7.49 (s, 4H), 7.71 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.1, 31.5, 34.8, 35.0, 52.4, 54.2, 54.6, (m), 119.8, 121.4, 123.1, (q, 1 J CF = 271 Hz), 125.8, 128.1, 128.2, (m), 129.1, 129.4, 132.1, 133.1, 134.8, 138.7, 139.3, 140.9, 151.1, 153.9, 154.5, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [18] + C 69 H 91 N + 8 : m/z ; found [2]Rotaxane 19 TFPB: 1,3-di-tert-butylbenzaldehyde (2.05 mg, 9.39 μmol) was added to a CHCl 3 solution mixture (471 μl) of the threadlike salt 16 TFPB (11.4 mg, 9.37 μmol) and the cyclophane 5 (4.51 mg, 9.38 μmol) and the solution mixture was stirred at 50 C for 16 h. The solution mixture was then slowly added to a MeOH S6
7 solution (941 μl) of NaBH 4 (7.12 mg, 188 μmol) and the organic solvents were removed under reduced pressure. The residue was partitioned between DI water (10 ml) and CH 2 Cl 2 (2 10 ml) and the combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (Diol-silica gel; CH 2 Cl 2 /hexanes, 3:7) to afford [2]rotaxane 19 TFPB as a colorless oil (7.7 mg, 43%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.23 (s, 18H), 1.33 (s, 18H), 3.81 (s, 4H), 4.43 (d, J = 10.6 Hz, 8H), 4.46 (d, J = 10.6 Hz, 8H), 6.31 (s, 2H), 6.46 (d, J = 7.8 Hz, 2H), 6.68 (s, 1H), (m, 12H), (m, 9H), 7.34 (s, 1H), 7.36 (s, 1H), 7.49 (s, 4H), 7.70 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.2, 31.5, 34.8, 35.0, 52.5, 54.1, 73.9, (m), 119.6, 121.3, 122.1, 123.0, (q, 1 J CF = 271 Hz), 125.8, 128.5, 128.8, 128.9, (m), 129.4, 130.5, 131.3, 134.8, 137.3, 138.9, 141.6, 151.0, 152.4, 153.2, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [19] + C 69 H 87 N 4 O + 4 : m/z ; found [2]Rotaxane 20 TFPB: 1,3-di-tert-butylbenzaldehyde (79.1 mg, mmol) was added to a CH 2 Cl 2 solution mixture (18.1 ml) of the guanidinium salt 16 TFPB (441 mg, mmol) and cyclophane 10 (173 mg, mmol) and the solution mixture was stirred at 50 C for 6 h. The solution mixture was then slowly added to a MeOH solution (36.2 ml) of NaBH 4 (274 mg, 7.24 mmol) and the organic solvents were evaporated under reduced pressure. The residue was partitioned between DI water (20 ml) and CH 2 Cl 2 (2 20 ml) and the combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (Diol-silica gel; CH 2 Cl 2 /hexanes, 7:3) to afford [2]rotaxane 20 TFPB as a colorless oil (60 mg, 9%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.34 (s, 36H), 3.61 (s, 2H), 3.65 (s, 8H), (m, 6H), 3.77(d, J = 12.7 Hz, 4H), 6.14 (d, J = 8.1 Hz, 2H), (br, 2H), 6.80 (s, 2H), 7.05 (m, 10H), 7.14 (d, J = 7.7 Hz, 4H), 7.17 (s, 2H), (m, 2H), 7.37 (s, 1H), 7.47 (s, 1H), 7.49 (s, 4H), 7.69 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.2, 31.5, 34.9, 35.2, 52.3, 53.4, 53.7, 54.1, (m), 119.4, 121.7, 122.2, 122.3, 123.1, (q, 1 J CF = 271 Hz), 124.6, 127.7, 128.1, 128.8, (m), 129.0, 129.1, 132.0, 133.0, 134.8, 138.4, 139.3, 151.2, 153.4, 154.2, (q, 1 J CB = 50 Hz) (one signal was missing, possibly because of signal overlap); HR-MS (ESI): calcd for [20] + C 69 H 91 N + 8 : m/z ; found [2]Rotaxane 21 TFPB: 1,3-di-tert-butylbenzaldehyde (17.1 mg, 78.3 μmol) was added to a CHCl 3 solution mixture (3.92 ml) of the guanidinium salt 16 TFPB (95.4 mg, 78.4 μmol) and cyclophane 13 (37.7 mg, 78.4 μmol) and the solution mixture was stirred at 50 C for 16 h. The solution mixture was then slowly added to a MeOH solution (7.85 ml) of NaBH 4 (59.4 mg, 1.57 mmol) and the organic solvents were S7
8 removed under reduced pressure. The residue was partitioned between DI water (10 ml) and CH 2 Cl 2 (2 10 ml) and the combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (Diol-silica gel; CH 2 Cl 2 /hexanes, 6:4) to afford [2]rotaxane 21 TFPB as a colorless oil (20.1 mg, 13%).; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.27 (s, 18H), 1.32 (s, 18H), 3.84 (s, 2H), 3.86 (s, 2H), 4.00 (br, 2H), 4.39 (d, J = 10.1 Hz, 4H), 4.44 (d, J = 10.1 Hz, 4H), 4.48 (d, J = 10.6 Hz, 4H), 4.53 (d, J = 10.6 Hz, 4H), 6.38 (s, 2H), 6.44 (br, 2H), 6.49 (d, J = 7.9 Hz, 2H), 6.89 (s, 8H), (m, 11H), 7.36 (s, 1H), 7.39 (s, 1H), 7.48 (s, 4H), 7.69 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.2, 31.5, 34.8, 35.1, 52.6, 54.2, 54.1, 73.5, (m), 119.6, 121.3, 122.2, 123.3, (q, 1 J CF = 271 Hz), 124.8, 127.5, 128.4, (m), 129.0, 129.2, 129.7, 130.5, 131.3, 134.8, 137.3, 137.9, 138.9, 141.6, 151.1, 152.1, 153.8, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [21] + C 69 H 87 N 4 O + 4 : m/z ; found Thiourea S4: 1,3-di-tert-butyl-5-isothiocyanatobenzene (50.2 mg, mmol) was added to a THF solution (2.01 ml) of 3,5-di-tert-butylbenzylaniline (41.3 mg, mmol) and the solution mixture was heated at 50 o C for 16 h. The organic solvent was removed under reduced pressure and the residue was purified chromatographically (SiO 2 ; CH 2 Cl 2 /hexanes, 4:6) to afford thiourea S4 as a pale yellow solid (55.0 mg, 60%).; M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.30 (s, 36H), 7.22 (s, 4H), 7.29 (s, 2H), 7.91 (br, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.3, 35.0, 119.0, 120.7, 136.5, 152.3, 179.1; HR-MS (ESI): calcd for [S4 + H] + C 29 H 45 N 2 S + : m/z ; found Guanidine S5: A DMF solution (6.41 ml) of thiourea S4 (301 mg; mmol) was cooled to 0 o C and sequentially added (35%; 133 mg, 151 μl, 1.33 mmol), triethylamine (269 mg, 371 μl,2.66 mmol), and HgCl 2 (361 mg, 1.33 mmol). The solution mixture was stirred virgrously at 0 o C. After the color turned black, the S8
9 solution mixture was slowly warmed to room temperature and stirred for 1 h. The solution suspension was then added CH 2 Cl 2 (40 ml) and filtered through Celite. The filtrate was concentrated and the residue was partitioned between H 2 O (40 ml) and CH 2 Cl 2 (2 40 ml). The combined organic layers were dried (MgSO 4 ), concentrated, and purified chromatographically (NH-silica gel; EtOAc/hexanes, 2:8) to afford guanidine S5 as a white solid (222 mg, 77%).; M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.27 (s, 36H), 6.94 (d, J = 1.5 Hz, 4H), 7.10 (s, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.4, 34.8, 117.4, 118.0, 143.1, 150.4, 151.8; HR-MS (ESI): calcd for [S5 + H] + C 29 H 46 N + 3 : m/z ; found Guanidinium Salt 22 TFPB: A CH 3 CN solution (8.00 ml) of guanidine S5 (118 mg, mmol) was added HCl (aq) (3N, 90.3 μl) and stirred at room temperature for 10 min. The solution mixture was then added NaTFPB (240 mg, mmol) and stirred for another 10 min. The organic solvent was removed under reduced pressure and the residue was partitioned between DI water (20 ml) and CH 2 Cl 2 (2 20 ml). The combined organic layers were dried (MgSO 4 ) and concentrated. The residue was purified chromatographically (SiO 2, CH 2 Cl 2 /hexanes, 1:1) and the product was precipitated in hexanes to afford guanidinium salt 22 TFPB as a pale yellow solid (302 mg, 86%); M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.31 (s, 36H), 5.56 (br, 2H), 7.13 (s, 4H), 7.29 (br, 2H), 7.56 (s, 4H) 7.61 (s, 2H), 7.76 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.0, 35.1, (m), 120.5, (q, 1 J CF = 271 Hz), 124.9, (m), 130.5, 134.8, 155.0, 155.2, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [22] + C 29 H 46 N + 3 : m/z ; found [2]Rotaxane 23 TFPB: A CHCl 3 solution mixture (442 μl) of the dumbbell-shaped salt 22 TFPB (11.5 mg, 8.85 μmol), 1,3-phenylenedimethanamine (3) (2.41 mg, 2.34 μl, 17.7 μmol) and isophthalaldehyde (2) (2.37 mg, 17.7 μmol) was stirred at 50 C for 10 d and the solution mixture was slowly added to a MeOH solution (1.77 ml) of NaBH 4 (13.4 mg, 354 μmol). The organic solvents were removed under reduced pressure and the residue was partitioned between DI water (10 ml) and CH 2 Cl 2 (2 10 ml). The combined organic layers were dried (MgSO 4 ), concentrated, and purified chromatographically (SiO 2 gel; CH 2 Cl 2 /hexanes, 7:3) to afford [2]rotaxane 23 TFPB as a white solid (12.6 mg, 80%).; M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.15 (s, 36H), 3.72 (s, 16H), 6.69 (s, 4H), 7.14 (d, J = 7.1 Hz, 8H), (m, 4H), 7.36 (s, 2H), 7.38 (s, 4H), 7.50 (s, 4H), 7.72 (s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.1, 35.0, 54.5, (m), 119.4, 122.8, (q, 1 J CF = 271 Hz), 128.1, 128.1, (m), 129.2, 133.3, 134.8, 139.3, 153.6, 154.1, (q, 1 J CB = 50 Hz); HR-MS (ESI): calcd for [23] + C 61 H 82 N + 7 : m/z ; S9
10 found [2]Rotaxane 24 TFPB: A CHCl 3 solution mixture (2.80 ml) of the dumbbell-shaped salt 22 TFPB (35.8 mg, mmol), 1,4-phenylenedimethanamine (11) (7.50 mg, mmol) and isophthalaldehyde (2) (7.39 mg, mmol) was stirred at 50 C for 72 h and then slowly added to a MeOH solution (11.0 ml) of NaBH 4 (83.3 mg, 2.20 mmol). The organic solvents were removed under reduced pressure and the residue was partitioned between DI water (20 ml) and CH 2 Cl 2 (2 20 ml). The combined organic layers were dried (MgSO 4 ), concentrated and purified chromatographically (SiO 2 gel; CH 2 Cl 2 /hexanes, 8:2) to afford [2]rotaxane 24 TFPB as a white solid (27.6 mg, 56%).; M.p. = C; 1 H NMR (400 MHz, CDCl 3 ): δ = 1.26 (s, 36H), 3.65 (s, 8H), 3.73 (s, 8H), 6.49 (d, J = 1.3 Hz, 4H), 6.97 (s, 8H), 7.14 (s, 2H), 7.22 (d, J = 7.3 Hz, 4H), (m, 3H), 7.41 (s, 2H), 7.50 (s, 4H), 7.70(s, 8H); 13 C NMR (100 MHz, CDCl 3 ): δ = 31.2, 35.1, 53.3, 53.6, (m), 118.2, 122.7, (q, 1 J CF = 271 Hz), 127.8, 127.9, (m), 128.9, 129.1, 132.6, 134.8, 139.1, 139.5, 152.9, 153.8, (q, 1 J CB = 49 Hz); HR-MS (ESI): calcd for [24] + C 61 H 82 N + 7 : m/z ; found Reference: [a] Xing, H.; Zhang, Y.; Lai, Y.; Jiang, Y.; Ma, D. J. Org. Chem., 2012, 77, S10
11 ppm S
12 ppm S12
13 ppm S13
14 ppm S14
15 ppm S15
16 ppm S16
17 ppm S17
18 ppm S18
19 ppm S19
20 ppm S20
21 ppm S21
22 ppm S22
23 ppm S23
24 ppm ppm S24
25 ppm S25
26 ppm ppm S26
27 ppm S27
28 ppm ppm S28
29 ppm S29
30 ppm S30
31 ppm S31
32 ppm S32
33 ppm S
34 ppm S34
35 ppm S35
36 ppm S36
37 ppm S37
38 ppm ppm S38
39 ppm S39
40 ppm ppm S40
41 ppm S41
42 ppm ppm S42
43 ppm S43
44 ppm ppm S44
45 ppm S45
46 ppm ppm S46
47 ppm S47
48 ppm ppm S48
49 ppm S
50 ppm ppm S50
51 ITC measurements were performed using a MicroCal MCS calorimeter interfaced with a microcomputer. All sample solutions were carefully degassed prior to titration using the equipment provided with the instrument. A solution of the cyclophane 1 or 5 (CHCl3) was titrated into a solution of the threadlike salt 9 TFPB (CHCl3) using a 280-μL syringe. Each titration consisted of a preliminary 10-μL injection followed by 27 subsequent additions of 10 μl. The entropy (ΔS o ) of the complexation was determined by subtracting the heat of dilution of each titration from the enthalpy (ΔH o ) of the titration. All the experiments were performed at 298 K. MicroCal LLC software was used to compute the thermodynamic parameters of the titration based on the one-site binding model. The Gibbs free energy (ΔG o ) was calculated from the binding constant using R = cal*k -1 *mol -1. Aliquouts (10 μl, 10 mm) of CHCl3 solution of the macrocycle 1 were titrated into stirring CHCl3 solution of the 9 TFPB (1 mm) at 298 K. Host M + Entry N K (M -1 ) ΔH o (cal*mol -1 ) ΔS o (cal*k -1 *mol -1 ) ΔG o (kcal*mol -1 ) ± E4 ± 6.13E ± ± 0.03 Threadlike Cyclophane ± E3 ± 5.43E ± ± 0.04 Salt ± E4 ± 4.05E ± ± TFPB Average ± E4 ± 5.27E ± ± ± 0.03 Aliquouts (10 μl, 20 mm) of CHCl3 solution of the cyclophane 5 were titrated into stirring CHCl3 solution of the 9 TFPB (2 mm) at 298 K. Host M + Entry N K (M -1 ) ΔH o (cal*mol -1 ) ΔS o (cal*k -1 *mol -1 ) ΔG o (kcal*mol -1 ) ± E3 ± 2.40E ± ± 0.06 Threadlike Cyclophane ± E3 ± 3.67E ± ± 0.07 Salt ± E3 ± 1.02E ± ± TFPB Average ± E3 ± 2.60E ± ± ± 0.06 S51
52 S52
53 S53
54 ITC measurements were performed using a MicroCal MCS calorimeter interfaced with a microcomputer. All sample solutions were carefully degassed prior to titration using the equipment provided with the instrument. A solution of the cyclophane 10 or 13 (CHCl3) was titrated into a solution of the threadlike salt 9 TFPB (CHCl3) using a 280-μL syringe. Each titration consisted of a preliminary 10-μL injection followed by 27 subsequent additions of 10 μl. The entropy (ΔS o ) of the complexation was determined by subtracting the heat of dilution of each titration from the enthalpy (ΔH o ) of the titration. All the experiments were performed at 298 K. MicroCal LLC software was used to compute the thermodynamic parameters of the titration based on the one-site binding model. The Gibbs free energy (ΔG o ) was calculated from the binding constant using R = cal*k -1 *mol -1. Aliquouts (10 μl, 12 mm) of CHCl3 solution of the cyclophane 10 were titrated into stirring CHCl3 solution of the 9 TFPB (0.8 mm) at 298 K. Host M + Entry N K (M -1 ) ΔH o (cal*mol -1 ) ΔS o (cal*k -1 *mol -1 ) ΔG o (kcal*mol -1 ) ± E3 ± 1.64E ± ± 0.08 Threadlike Cyclophane ± E3 ± 1.17E ± ± 0.05 Salt ± E3 ± 2.19E ± ± TFPB Average ± E3 ± 1.72E ± ± ± 0.08 Aliquouts (10 μl, 18 mm) of CHCl3 solution of the cyclophane 13 were titrated into stirring CHCl3 solution of the 9 TFPB (1.2 mm) at 298 K. Host M + Entry N K (M -1 ) ΔH o (cal*mol -1 ) ΔS o (cal*k -1 *mol -1 ) ΔG o (kcal*mol -1 ) ± E2 ± 1.4E ± ± 0.12 Threadlike Cyclophane ± E2 ± 1.25E ± ± 0.14 Salt ± E2 ± 9.85E ± ± TFPB Average ± E2 ± 1.22E ± ± ± 0.11 S54
55 S55
56 S56
57 S57
58 S58
59 Competition experiment for the cyclophane 1 and 5 with threadlike salt 9 TFPB a) b) c) 1 H NMR spectra (400 MHz, CDCl 3, 298 K) of a) an equimolar mixture (10 mm) of 1 and 9 TFPB, b) an equimolar mixture of 1, 5, and 9 TFPB, c) an equimolar mixture of 5 and 9 TFPB Complexation ratio for b) Tetraaza-cyclophane 1: δ δ(free) δ(shift) = = = 76% δ(max) D Tetraoxo-cyclophane 5: δ δ(free) δ(shift) = = = 23% δ(max) D S59
60 Competition experiment for the cyclophane 10 and 13 with threadlike salt 9 TFPB a) b) c) 1 H NMR spectra (400 MHz, CDCl 3, 298 K) of a) an equimolar mixture (10 mm) of 10 and 9 TFPB, b) an equimolar mixture of 10, 13, and 9 TFPB, c) an equimolar mixture of 10 and 9 TFPB Complexation ratio for b) Tetraaza-cyclophane 10: δ δ(free) δ(shift) = = = 62% δ(max) D Tetraoxo-cyclophane 13: δ δ(free) δ(shift) = = = 37% δ(max) D S60
61 (a) O H (b) N Ar H Ar N H (c) D R D R (d) D R N R H H N D R (e) R N H Ar-CH 2 -N H NMR spectra (400 MHz, CDCl 3, 298 K) of an equimolar mixture of the threadlike salt 16-TFPB, the tetraaza-cyclophane 1, and the aldehyde 17 that had been heated at 323 K for (a) 0, (b) 10, (c) 30, (d) 90, and (e) 540 min. D and R denote signals representing the dumbbell-shaped salt and the [2]rotaxane, respectively. S61
62 S62
63 S63
64 S64
65 S65
66 [18] + = C 69 H 91 N 8 + = S66
67 +TOF MS: 9 MCA scans from Sample 1 of chiu-YHC-Rtx233-3.wiff a= e-004, t0= e+001 R; (Nanospray) Max. 2.5e4 counts. I n t e n s i t y, c o u n t s 2.4e4 2.2e4 2.0e4 1.8e4 1.6e4 1.4e4 1.2e4 1.0e [19] + = C 69 H 87 N 4 O 4 + = m/z, Da S67
68 +TOF MS: 12 MCA scans from Sample 1 of chiu-YHC-pNrtx-3.wiff a= e-004, t0= e+001 R; (Nanospray) Max. 2.3e4 counts. In te n s ity, c o u n ts 2.3e4 2.2e4 2.1e4 2.0e4 1.9e4 1.8e4 1.7e4 1.6e4 1.5e4 1.4e4 1.3e4 1.2e4 1.1e4 1.0e [20] + = C 69 H 91 N 8 + = m/z, Da S68
69 +TOF MS: 13 MCA scans from Sample 1 of chiu-YJL threasing-p-O-rtx-3.wiff a= e-004, t0= e+001 (Nanospray) Max. 1.4e4 counts. I n t e n s i t y, c o u n t s 1.4e4 1.3e4 1.2e4 1.1e4 1.0e [21] + = C 69 H 87 N 4 O 4 + = m/z, Da S69
70 [23] + = C 61 H 82 N 7 + = S70
71 [24] + = C 61 H 82 N 7 + = S71
Preparation of Stable Aziridinium Ions and Their Ring Openings
Supplementary Information Preparation of Stable Aziridinium Ions and Their Ring Openings Yongeun Kim a Hyun-Joon Ha*, a Sae Young Yun b and Won Koo Lee,*,b a Department of Chemistry and Protein Research
More informationp-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of
Supporting Information for: p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN 3 for Synthesis of 4-Aryl-NH-1,2,3-triazoles Xue-Jing Quan, Zhi-Hui Ren, Yao-Yu Wang, and
More informationSupporting Information
Supporting Information Synthesis of N-Heteropolycyclic Compounds Including Quinazolinone Skeletons by Using Friedel-Crafts Alkylation Bu Keun Oh, Eun Bi Ko, Jin Wook Han* and Chang Ho Oh* Department of
More informationMasatoshi Shibuya,Takahisa Sato, Masaki Tomizawa, and Yoshiharu Iwabuchi* Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences,
Oxoammonium ion/naclo 2 : An Expedient, Catalytic System for One-pot Oxidation of Primary Alcohols to Carboxylic Acid with Broad Substrate Applicability Masatoshi Shibuya,Takahisa Sato, Masaki Tomizawa,
More informationSupporting Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2018 Supporting Information Facile Three-Step Synthesis and Photophysical Properties of [8]-, [9]-,
More informationSupporting Information for. Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the. analysis of Glucose in Whole Blood
Supporting Information for Boronic Acid Functionalized Aza-Bodipy (azabdpba) based Fluorescence Optodes for the analysis of Glucose in Whole Blood Yueling Liu, Jingwei Zhu, Yanmei Xu, Yu Qin*, Dechen Jiang*
More informationSupporting Information for. Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of. 3,5-Disubstituted Pyridines: Mechanistic Studies
Supporting Information for Use of the Curtius Rearrangement of Acryloyl Azides in the Synthesis of 3,5-Disubstituted Pyridines: Mechanistic Studies Ta-Hsien Chuang* a, Yu-Chi Chen b and Someshwar Pola
More informationSupporting Information. Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base
Supporting Information Efficient copper-catalyzed Michael addition of acrylic derivatives with primary alcohols in the presence of base Feng Wang, a Haijun Yang, b Hua Fu, b,c * and Zhichao Pei a * a College
More informationSupporting Information. for. Access to pyrrolo-pyridines by gold-catalyzed. hydroarylation of pyrroles tethered to terminal alkynes
Supporting Information for Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes Elena Borsini 1, Gianluigi Broggini* 1, Andrea Fasana 1, Chiara Baldassarri
More informationA pillar[2]arene[3]hydroquinone which can self-assemble to a molecular zipper in the solid state
A pillar[2]arene[3]hydroquinone which can self-assemble to a molecular zipper in the solid state Mingguang Pan, Min Xue* Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China Fax:
More informationRegioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation
Regioective Halogenation of 2-Substituted-1,2,3-Triazole via sp 2 C-H Activation Qingshan Tian, Xianmin Chen, Wei Liu, Zechao Wang, Suping Shi, Chunxiang Kuang,* Department of Chemistry, Tongji University,
More informationSupporting Information. Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as
Supporting Information Palladium-Catalyzed Formylation of Aryl Iodides with HCOOH as CO Source Guanglong Sun,,, Xue Lv,,, Yinan Zhang, Min Lei,*,, and Lihong Hu*, Jiangsu Key Laboratory for Functional
More informationEthyl 2-hydroxy-4-methyl-1-((prop-2-yn-1-yloxy)methyl)cyclohex-3-enecarboxylate (16):
General methods: 1 H NMR and 13 C NMR spectra were recorded in CDCl 3 or CDCl3 and CCl 4 as solvent on 300 MHz or 500 MHz spectrometer at ambient temperature. The coupling constant J is given in Hz. The
More informationSynthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice
Supporting Information Rec. Nat. Prod. 9:4 (2015) 561-566 Synthesis and Blastocyst Implantation Inhibition Potential of Lupeol Derivatives in Female Mice Anita Mahapatra 1*, Purvi Shah 1, Mehul Jivrajani
More informationThiol-Activated gem-dithiols: A New Class of Controllable. Hydrogen Sulfide (H 2 S) Donors
Thiol-Activated gem-dithiols: A New Class of Controllable Hydrogen Sulfide (H 2 S) Donors Yu Zhao, Jianming Kang, Chung-Min Park, Powell E. Bagdon, Bo Peng, and Ming Xian * Department of Chemistry, Washington
More informationElectronic Supplementary Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2015 Electronic Supplementary Information ovel pseudo[2]rotaxanes constructed by selfassembly of dibenzyl
More informationElectronic Supplementary Information
Electronic Supplementary Information A Novel and Facile Zn-mediated Intramolecular Five-membered Cyclization of β-tetraarylporphyrin Radicals from β-bromotetraarylporphyrins Dong-Mei Shen, Chao Liu, Qing-Yun
More informationmm C3a. 1 mm C3a Time (s) C5a. C3a. Blank. 10 mm Time (s) Time (s)
125 I-C5a (cpm) Fluorescnece Em 520nm a 4000 3000 2000 1000 c 0 5000 4000 3000 2000 Blank C5a C3a 6 0.3 mm C3a 7 9 10 11 12 13 15 16 0.3 mm C5a 0 300 600 900 1200 Time (s) 17 Fluorescnece Em 520nm Fluorescnece
More informationSupporting Information
Ferrocene Amino Acid Macrocycles as Hydrazone Based Receptors for Anions Sophie R. Beeren and Jeremy K. M. Sanders Supporting Information S1 Experimental 2 S1.1 General Experimental Procedures 2 S1.2 Synthesis
More informationLewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines
Supporting Information for Lewis acid-catalyzed regioselective synthesis of chiral α-fluoroalkyl amines via asymmetric addition of silyl dienolates to fluorinated sulfinylimines Yingle Liu a, Jiawang Liu
More informationDivergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes
Divergent Construction of Pyrazoles via Michael Addition of N-Aryl Hydrazones to 1,2-Diaza-1,3-dienes Serena Mantenuto, Fabio Mantellini, Gianfranco Favi,* and Orazio A. Attanasi Department of Biomolecular
More informationSupporting Information. for. Pd-catalyzed decarboxylative Heck vinylation of. 2-nitro-benzoates in the presence of CuF 2
Supporting Information for Pd-catalyzed decarboxylative Heck vinylation of 2-nitro-benzoates in the presence of CuF 2 Lukas J. Gooßen*, Bettina Zimmermann, Thomas Knauber Address: Department of Chemistry,
More informationph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors
ph Switchable and Fluorescent Ratiometric Squarylium Indocyanine Dyes as Extremely Alkaline Sensors Jie Li, Chendong Ji, Wantai Yang, Meizhen Yin* State Key Laboratory of Chemical Resource Engineering,
More informationManganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature
Supplementary Information Manganese powder promoted highly efficient and selective synthesis of fullerene mono- and biscycloadducts at room temperature Weili Si 1, Xuan Zhang 1, Shirong Lu 1, Takeshi Yasuda
More informationSupporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylin
Supporting Information Synthesis of 2-Aminobenzonitriles through Nitrosation Reaction and Sequential Iron(III)-Catalyzed C C Bond Cleavage of 2-Arylindoles Wei-Li Chen, Si-Yi Wu, Xue-Ling Mo, Liu-Xu Wei,
More informationAn Unusual Glycosylation Product from a Partially Protected Fucosyl Donor. under Silver Triflate activation conditions. Supporting information
An Unusual Glycosylation Product from a Partially Protected Fucosyl Donor under Silver Triflate activation conditions Robin Daly a and Eoin M. Scanlan* a e-mail: eoin.scanlan@tcd.ie a Trinity Biomedical
More informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Supporting Information Enantioselective Cu-catalyzed 1,4-Addition of Various Grignard Reagents to Cyclohexenone using Taddol-derived Phosphine-Phosphite
More informationElectronic Supplementary Information. Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of
Electronic Supplementary Information Quinine/Selectfluor Combination Induced Asymmetric Semipinacol Rearrangement of Allylic Alcohols: An Effective and Enantioselective Approach to α Quaternary β Fluoro
More informationDirect ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle
Direct ortho-c H Functionalization of Aromatic Alcohols Masked by Acetone Oxime Ether via exo-palladacycle Kun Guo, Xiaolan Chen, Mingyu Guan, and Yingsheng Zhao* Key Laboratory of Organic Synthesis of
More informationSchwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins
Electronic Supplementary Information (ESI) Schwartz s reagent-mediated regiospecific synthesis of 2,3-disubstituted indoles from isatins A. Ulikowski and B. Furman* Institute of Organic Chemistry, Polish
More informationSUPPORTING INFORMATION
Energetically Demanding Transport in a Supramolecular Assembly Chuyang Cheng, Paul R. McGonigal, Wei-Guang Liu, Hao Li, Nicolaas A. Vermeulen, Chenfeng Ke, Marco Frasconi, Charlotte L. Stern, William A.
More informationSupporting Information. Radical fluorination powered expedient synthesis of 3 fluorobicyclo[1.1.1]pentan 1 amine
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information Radical fluorination powered expedient synthesis
More informationSupplemental Material
Supplemental Material General Methods Unless otherwise indicated, all anhydrous solvents were commercially obtained and stored under nitrogen. Reactions were performed under an atmosphere of dry nitrogen
More informationSupporting information
Supporting information Diversity Oriented Asymmetric Catalysis (DOAC): Stereochemically Divergent Synthesis of Thiochromanes Using an Imidazoline-aminophenol aminophenol (IAP)-Ni Catalyzed Michael/Henry
More informationGraduate School of Nutritional and Environmental Sciences, University of Shizuoka,
Identification of Indole Alkaloid Structural Units Important for Stimulus Selective TRPM8 Inhibition: SAR Study of Naturally Occurring Iboga Derivatives Yuko Terada,, Mariko Kitajima,, Fuyumi Taguchi,
More informationEur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2009 ISSN X SUPPORTING INFORMATION
Eur. J. rg. Chem. 2009 WILEY-VC Verlag Gmb & Co. KGaA, 69451 Weinheim, 2009 ISS 1434 193X SUPPRTIG IFRMATI Title: ew GM1 Ganglioside Derivatives for Selective Single and Double Labelling of the atural
More informationStructure and conserved function of iso-branched sphingoid bases from the nematode Caenorhabditis elegans
Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 207 Structure and conserved function of iso-branched sphingoid bases from the nematode Caenorhabditis
More informationRuthenium-Catalyzed C H Oxygenation on Aryl Weinreb Amides
Supporting Information Ruthenium-Catalyzed C H xygenation on Aryl Weinreb Amides Fanzhi Yang and Lutz Ackermann* Institut für rganische und Biomolekulare Chemie Georg-August-Universität Tammannstrasse
More informationSUPPORTING INFORMATION
SUPPORTING INFORMATION Exploiting the Ring Strain in Bicyclo[2.2.1]heptane Systems for the Stereoselective Preparation of Highly Functionalized Cyclopentene, Dihydrofuran, Pyrroline and Pyrrolidine Scaffolds
More information3016 Oxidation of ricinoleic acid (from castor oil) with KMnO 4 to azelaic acid
6 Oxidation of ricinoleic acid (from castor oil) with KMnO 4 to azelaic acid CH -(CH ) OH (CH ) -COOH KMnO 4 /KOH HOOC-(CH ) -COOH C H 4 O (.) KMnO 4 KOH (.) (6.) C H 6 O 4 (.) Classification Reaction
More informationScheme S1. Synthesis of glycose-amino ligand.
Scheme S1. Synthesis of glycose-amino ligand. 5-Chloro-1-pentyl-2,3,4,6-tetra-O-acetyl-ß-D-glucopyranoside S2 To a solution of penta-o-acetyl-ß-d-glucopyranoside S1 (3.0 g, 7.69 mmol) and 5-chloropentan-1-ol
More informationDirect Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source
Direct Aerobic Carbonylation of C(sp 2 )-H and C(sp 3 )-H Bonds through Ni/Cu Synergistic Catalysis with DMF as the Carbonyl Source Xuesong Wu, Yan Zhao, and Haibo Ge* Table of Contents General Information...
More information# Supplementary Material (ESI) for Chemical Communications # This journal is The Royal Society of Chemistry 2005
Electronic Supplementary Information for: (Z)-Selective cross-dimerization of arylacetylenes with silylacetylenes catalyzed by vinylideneruthenium complexes Hiroyuki Katayama,* Hiroshi Yari, Masaki Tanaka,
More informationSupporting Information. An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization
Supporting Information An Efficient Synthesis of Optically Active Physostigmine from Tryptophan via Alkylative Cyclization Michiaki, Kawahara, Atsushi Nishida, Masako Nakagawa* Faculty of Pharmaceutical
More informationSupporting Information. as the nitro source
Supporting Information Efficient ipso-nitration of arylboronic acids with iron nitrate as the nitro source Min Jiang, a,b Haijun Yang,* a,b Yong Li, a,b Zhiying Jia b and Hua Fu b a Beijing Key Laboratory
More informationElectronic Supplementary Information
Electronic Supplementary Information ~ Experimental Procedures and Spectral/Analytical Data ~ Use of Dimethyl Carbonate as a Solvent Greatly Enhances the Biaryl Coupling of Aryl Iodides and Organoboron
More informationRameshwar Prasad Pandit and Yong Rok Lee * School of Chemical Engineering, Yeungnam University, Gyeongsan , Korea
Electronic Supplementary Material (ESI) for rganic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2014 Novel ne-pot Synthesis of Diverse γ,δ-unsaturated β-ketoesters by Thermal
More informationAll chemicals were obtained from Aldrich, Acros, Fisher, or Fluka and were used without
Supplemental Data Alexander et al. Experimental Procedures General Methods for Inhibitor Synthesis All chemicals were obtained from Aldrich, Acros, Fisher, or Fluka and were used without further purification,
More informationNitro-Grela-type complexes containing iodides. robust and selective catalysts for olefin metathesis
Supporting Information for Nitro-Grela-type complexes containing iodides robust and selective catalysts for olefin metathesis under challenging conditions. Andrzej Tracz, 1,2 Mateusz Matczak, 1 Katarzyna
More informationSupporting Information. Nitrodibenzofuran: a One- and Two-Photon Sensitive Protecting Group that is Superior to
Supporting Information Nitrodibenzofuran: a One- and Two-Photon Sensitive Protecting Group that is Superior to Brominated Hydroxycoumarin for Thiol Caging in Peptides M. Mohsen Mahmoodi, Daniel Abate-Pella,
More informationStereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines
Stereoselective Aza-Darzens Reactions of Tert- Butanesulfinimines: Convenient Access to Chiral Aziridines Toni Moragas Solá, a Ian Churcher, b William Lewis a and Robert A. Stockman* a Supplementary Information
More informationChristophe Lincheneau, Bernard Jean-Denis and Thorfinnur Gunnlaugsson* Electronic Supplementary Information
Self-assembly formation of mechanically interlocked [2]- and [3]catenanes using lanthanide ion [Eu(III)] templation and ring closing metathesis reactions Christophe Lincheneau, Bernard Jean-Denis and Thorfinnur
More informationSupporting Information
Supporting Information for Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5- tetrafluorocyclohexane Mohammed Salah Ayoup 1,2, David B. Cordes 1,
More informationSupporting Information
Supporting Information B(C 6 F 5 ) 3 -catalyzed Regioselective Deuteration of Electronrich Aromatic and Heteroaromatic compounds Wu Li, Ming-Ming Wang, Yuya Hu and Thomas Werner* Leibniz-Institute of Catalysis
More informationCDI Mediated Monoacylation of Symmetrical Diamines and Selective Acylation of Primary Amines of Unsymmetrical Diamines
Supporting information: CDI Mediated Monoacylation of Symmetrical Diamines and Selective Acylation of Primary Amines of Unsymmetrical Diamines Sanjeev K. Verma*, Ramarao Ghorpade, Ajay Pratap and M. P.
More informationSupporting Information. for. Synthesis of dye/fluorescent functionalized. dendrons based on cyclotriphosphazene
Supporting Information for Synthesis of dye/fluorescent functionalized dendrons based on cyclotriphosphazene Aurélien Hameau 1,2, Sabine Fuchs 1,2, Régis Laurent 1,2, Jean-Pierre Majoral* 1,2 and Anne-Marie
More informationThermal shift binding experiments were carried out using Thermofluor 384 ELS system. Protein
Supplementary Methods Thermal shift assays Thermal shift binding experiments were carried out using Thermofluor 384 ELS system. Protein unfolding was examined by monitoring the fluorescence of ANS (1-anilinonaphthalene-8-
More informationCopyright Wiley-VCH Verlag GmbH, D Weinheim, Angew. Chem
Copyright Wiley-VCH Verlag GmbH, D-69451 Weinheim, 2000. Angew. Chem. 2000. Supporting Information for Salen as Chiral Activator : Anti vs Syn Switchable Diastereoselection in the Enantioselective Addition
More informationSupporting Information
Investigation of self-immolative linkers in the design of hydrogen peroxide metalloprotein inhibitors Jody L. Major Jourden, Kevin B. Daniel, and Seth M. Cohen* Department of Chemistry and Biochemistry,
More informationCu-Catalyzed Direct C6-Arylation of Indoles
Cu-Catalyzed Direct C6-Arylation of Indoles (Supporting Information) Youqing Yang, Ruirui Li, Yue Zhao, Dongbing Zhao, and Zhuangzhi Shi*, State Key Laboratory of Coordination Chemistry, Collaborative
More informationAnalysis of fatty acid metabolism using Click-Chemistry and HPLC-MS
Analysis of fatty acid metabolism using Click-Chemistry and HPLC-MS Alexander J. Pérez and Helge B. Bode -Supporting Information- Contents Experimental section Supplementary figures NMR spectra Page S2
More informationSupporting Information for
S 1 Supporting Information for Novel and Convenient Synthesis of Substituted Quinolines by Copper or PalladiumCatalyzed Cyclodehydration of 1-(2-Aminoaryl)-2-yn-1-ols Bartolo Gabriele,*, Raffaella Mancuso,
More informationSUPPORTING INFORMATION FOR. Regioselective Ring-opening and Isomerization Reactions of 3,4-Epoxyesters Catalyzed by Boron Trifluoride
S1 SUPPORTING INFORMATION FOR Regioselective Ring-opening and Isomerization Reactions of 3,4-Epoxyesters Catalyzed by Boron Trifluoride Javier Izquierdo, Santiago Rodríguez and Florenci V. González* Departament
More informationElectronic Supplementary Material
Electronic Supplementary Material PAMAM Dendrimers Bearing Electron-Donating Chromophores: Fluorescence and Electrochemical Properties Bing-BingWang a, Xin Zhang a, Ling Yang a, Xin-Ru Jia* a, Yan Ji a,
More informationNHC-catalyzed cleavage of vicinal diketones and. triketones followed by insertion of enones and
Supporting Information for NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones Ken Takaki*, Makoto Hino, Akira Ohno, Kimihiro Komeyama, Hiroto Yoshida
More informationSupporting Information. Recyclable hypervalent-iodine-mediated solid-phase peptide
Supporting Information Recyclable hypervalent-iodine-mediated solid-phase peptide synthesis and cyclic peptide synthesis Dan Liu, Ya-Li Guo, Jin Qu and Chi Zhang* for Address: State Key Laboratory of Elemento-Organic
More informationA multicomponent CuAAC click approach. to a library of hybrid polydentate 2-pyridyl- the generation of metallosupramolecular. architectures.
Supporting information A multicomponent CuAAC click approach to a library of hybrid polydentate 2-pyridyl- 1,2,3-triazole ligands: New building blocks for the generation of metallosupramolecular architectures.
More informationSUPPLEMENTARY MATERIAL
SUPPLEMENTARY MATERIAL Chemical constituents from Agrimonia pilosa Ledeb. and their chemotaxonomic significance Wei-jie Liu, Xue-qian Hou, Hao Chen, Jing-yu Liang*, Jian-bo Sun** Department of Natural
More informationSupporting Information. Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition
Supporting Information Copper-catalyzed cascade synthesis of benzimidazoquinazoline derivatives under mild condition Shan Xu, Juyou Lu and Hua Fu* Key Laboratory of Bioorganic Phosphorus Chemistry and
More informationCatalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds
Catalytic decarboxylative alkylation of β-keto acids with sulfonamides via the cleavage of carbon nitrogen and carbon carbon bonds Cui-Feng Yang, Jian-Yong Wang and Shi-Kai Tian* Joint Laboratory of Green
More informationSupporting information for. Synthesis of phenothiazines from cyclohexanones and. 2-aminobenzenethiols under transition-metal-free conditions
Supporting information for Synthesis of phenothiazines from cyclohexanones and 2-aminobenzenethiols under transition-metal-free conditions Yunfeng Liao, a Pengcheng Jiang, a Shanping Chen, a Fuhong Xiao,
More informationSupplementary Material. Efficient Synthesis of an Indinavir Precursor from Biomass Derived (-)- Levoglucosenone
1.171/CH17227_AC CSIRO 217 Australian Journal of Chemistry 217, 7(1), 1146-115 Supplementary Material Efficient Synthesis of an Indinavir Precursor from Biomass Derived (-)- Levoglucosenone Edward T. Ledingham,
More informationSupporting Information
Supporting Information Direct Synthesis of Benzimidazoles by Dehydrogenative Coupling of Aromatic Diamines and Alcohols Catalyzed by Cobalt Prosenjit Daw, Yehoshoa Ben-David, and David Milstein* Department
More informationAllenylphosphine oxides as simple scaffolds for. phosphinoylindoles and phosphinoylisocoumarins
Supporting Information for Allenylphosphine oxides as simple scaffolds for phosphinoylindoles and phosphinoylisocoumarins G. Gangadhararao, Ramesh Kotikalapudi, M. Nagarjuna Reddy and K. C. Kumara Swamy*
More informationEfficient Metal-Free Pathway to Vinyl Thioesters with Calcium Carbide as the Acetylene Source
Electronic Supplementary Material (ESI) for Green Chemistry. This journal is The Royal Society of Chemistry 2015 Supporting Information Efficient Metal-Free Pathway to Vinyl Thioesters with Calcium Carbide
More informationSupporting Information for
Supporting Information for Tandem Mass Spectrometry Assays of Palmitoyl Protein Thioesterase and Tripeptidyl Peptidase Activity in Dried Blood Spots for the Detection of Neuronal Ceroid Lipofuscinoses
More informationElectronic Supplementary Information
Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information [Fe III (TF4DMAP)OTf] Catalysed Anti-Markovnikov Oxidation
More informationChemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis
Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of 3-Methylene-1,2-diazetidines: Application to Vicinal Diamine Synthesis Greg P. Iacobini, a David W. Porter, b and Michael Shipman* a a Department
More informationAn Orthogonal Array Optimization of Lipid-like Nanoparticles for. mrna Delivery in Vivo
Supporting Information An rthogonal Array ptimization of Lipid-like Nanoparticles for mrna Delivery in Vivo Bin Li, Xiao Luo, Binbin Deng, Junfeng Wang, David W. McComb, Yimin Shi, Karin M.L. Gaensler,
More informationSupporting Information
Electronic Supplementary Material (ESI) for rganic Chemistry Frontiers. This journal is the Partner rganisations 2016 Supporting Information Fangyi Li, Changgui Zhao, and Jian Wang* Department of Pharmacology
More informationNaoya Takahashi, Keiya Hirota and Yoshitaka Saga* Supplementary material
Supplementary material Facile transformation of the five-membered exocyclic E-ring in 13 2 -demethoxycarbonyl chlorophyll derivatives by molecular oxygen with titanium oxide in the dark Naoya Takahashi,
More informationPreparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF
Supporting information Preparation of Fluorinated Tetrahydropyrans and Piperidines using a New Nucleophilic Fluorination Reagent DMPU/HF Otome E. Okoromoba, a Gerald B. Hammond, a, * Bo Xu b, * a Department
More informationOrvinols with Mixed Kappa/Mu Opioid Receptor Agonist Activity
Supporting Information Orvinols with Mixed Kappa/Mu Opioid Receptor Agonist Activity Greedy, Benjamin M.; Bradbury, Faye.; Thomas, Mark P.; Grivas, Konstantinos; Cami-Kobeci, Gerta; Archambeau, Ashley.;
More informationSupporting Information
Supporting Information Wiley-VCH 2008 69451 Weinheim, Germany Enantioselective Rhodium-catalyzed Addition of Arylboronic Acids to α-ketoesters Hai-Feng Duan, Jian-Hua Xie, Xiang-Chen Qiao, Li-Xin Wang,
More informationSupplementary Information
Supplementary Information Ruthenium(IV) porphyrin catalyzed phosphoramidation of aldehyde with phosphoryl azide as nitrene source Wenbo Xiao, Cong-Ying Zhou and Chi-Ming Che* Department of Chemistry, State
More informationEur. J. Org. Chem WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2007 ISSN X SUPPORTING INFORMATION
Eur. J. Org. Chem. 2007 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 ISSN 1434 193X SUPPORTING INFORMATION Title: Effect of Varying the Anionic Component of a Copper(I) Catalyst on Homologation
More informationSupporting Information: Cis-to-Trans Isomerization of Azobenzene Investigated by Using Thin Films of Metal-Organic Frameworks
Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the wner Societies 2015 Supporting Information: Cis-to-Trans Isomerization of Azobenzene Investigated by
More informationDevelopment of a near-infrared fluorescent probe for monitoring hydrazine in serum and living cells
Supporting Information for Development of a near-infrared fluorescent probe for monitoring hydrazine in serum and living cells Sasa Zhu, Weiying Lin,* Lin Yuan State Key Laboratory of Chemo/Biosensing
More informationL-Carnosine-Derived Fmoc-Tripeptides Forming ph- Sensitive and Proteolytically Stable Supramolecular
Supporting Information: L-Carnosine-Derived Fmoc-Tripeptides Forming ph- Sensitive and Proteolytically Stable Supramolecular Hydrogels Rita Das Mahapatra, a Joykrishna Dey* a, and Richard G. Weiss b a
More informationSUPPLEMENTARY INFORMATION
SUPPLEMENTARY INFORMATION Synthesis of polyynes to model the sp-carbon allotrope carbyne Wesley A. Chalifoux and Rik R. Tykwinski, Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G
More informationSupplementary Information
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry B. This journal is The Royal Society of Chemistry 2017 Supplementary Information Geometrical Confinement Directed Albumin-Based
More informationSupporting Information. Ruthenium(II)-Catalyzed C H Alkynylation of Weakly-Coordinating Benzoic Acids. Ruhuai Mei, Shou-Kun Zhang, and Lutz Ackermann*
Supporting Information Ruthenium(II)-Catalyzed C H Alkynylation of Weakly-Coordinating Benzoic Acids Ruhuai Mei, Shou-Kun Zhang, and Lutz Ackermann* Institut für Organische und Biomolekulare Chemie, Georg-August-Universität
More informationA Hierarchy of Aryloxide Deprotection by Boron Tribromide. Supporting Information
A Hierarchy of Aryloxide Deprotection by Boron Tribromide Sreenivas Punna, Stéphane Meunier and M. G. Finn* Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute,
More informationImproved Carbonylation of Heterocyclic Chlorides and Challenging Aryl Bromides
Albaneze-Walker et al S-1 Improved Carbonylation of Heterocyclic Chlorides and Challenging Aryl Bromides Jennifer Albaneze-Walker*, Charles Bazaral, Tanya Leavey, Peter G. Dormer, and Jerry A. Murry Department
More informationPalladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation
1 Palladium(II)-Catalyzed Cross-Coupling of Simple Alkenes with Acrylates: A Direct Approach to 1,3-Dienes through C H Activation Zhen-Kang Wen, Yun-He Xu* and Teck-Peng Loh* Division of Chemistry and
More informationSupplementary Information
Supplementary Information Selective monomethylation of primary amines with simple electrophiles Thomas LEBLEU, Xiaolu MA, Jacques MADDALUNO and Julien LEGROS * General remarks 1 H NMR spectra were obtained
More informationAccessory Publication
10.1071/CH09088_AC CSIRO 2009 Accessory Publication: Australian Journal of Chemistry, 2009, 62(8), 790 793 Thermally Responsive Elastomeric Supramolecular Polymers Featuring Flexible Aliphatic Hydrogen
More informationyellow coloured amorphous powder, which on crystallization from hot acetone resulted in pale
Supporting Information Hexane Extract. Compound I: Elution of column with hexane: dichloromethane (50:50 v/v; 200 ml), gave a pale yellow coloured amorphous powder, which on crystallization from hot acetone
More informationNovel D-erythro N-Octanoyl Sphingosine Analogs As Chemo- and Endocrine. Resistant Breast Cancer Therapeutics
Page 11 of 32 Cancer Chemotherapy and Pharmacology Novel D-erythro N-Octanoyl Sphingosine Analogs As Chemo- and Endocrine Resistant Breast Cancer Therapeutics James W. Antoon, Jiawang Liu, Adharsh P. Ponnapakkam,
More informationNature Chemical Biology: doi: /nchembio.1721
Synthesis of β-lactone probes. General experimental. Tetrahydrofuran (THF) was dried using a solvent dispensing system (SDS) with a column of neutral alumina. Pyridine, toluene, dimethylformamide (DMF),
More information