Compound S23
Ethyl (EZ)-2-(2-(3-(3'-formyl-3-methyl-[1,1'-biphenyl]-4-yl)-6-(3'-(formyl-d)-3-methyl-[1,1'-biphenyl]-4-yl)quinolin-8-yl)hydrazono)-2-(5-(3-(3-((3-(2-((E)-4-methoxybenzylidene)hydrazinyl)-3-oxopropyl)disulfanyl)propoxy)phenyl)pyridin-2-yl)acetate
From: Pick-up, transport and release of a molecular cargo using a small-molecule robotic arm
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InChIKey ZGLCMHZPNVIKHU-BPSZAQQQSA-N
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
To a solution of S22 (50 mg, 50.80 µmol, 1.0 eq) in CH2Cl2 (800 µL) was added a solution of AcOH (3.0 µL, 50.80 µmol, 1.0 eq) in CH2Cl2 (90 µL) followed by cargo S7 (16 mg, 67.20 µmol, 1.3 eq). The reaction was stirred at r. t. for 16 h, then partitioned between CH2Cl2 (10 mL) and saturated sodium bicarbonate solution (10 mL). The aqueous phase was separated and extracted with CH2Cl2 (2 × 20 mL), dried (Na2SO4) and the solvent removed under reduced pressure. The crude reaction mixture was purified by flash column chromatography (SiO2, EtOAc/CH2Cl2 (0.2% Et3N), 5% → 20%) to give the desired product as an orange foam (45 mg, 40.64 µmol, 80%). 1H NMR (600 MHz, CD2Cl2, ~7:3 ratio of E-S23:Z-S23, each isomer exists as a ~87:13 ratio of cis:trans acyl hydrazone rotamers, major rotamers reported) δ 15.73 (s, 1H, HnE), 13.24 (s, 1H, HnZ), 10.12 (s, 1H, HaZ), 10.11 (s, 1H, HaE), 9.17 (d, J = 2.4 Hz, 1H, HyE), 9.03 (d, J = 2.1 Hz, 1H, HjE), 8.98 (d, J = 2.2 Hz, 1H, HjZ), 8.84 (d, J = 2.3 Hz, 1H, HyZ), 8.77 (s, 1H, HakZ), 8.70 (s, 1H, HakE), 8.26 (d, J = 8.4 Hz, 1H, HaaE), 8.23–8.17 (m, 6H, HbE+bZ+kE+kZ+sE+sZ), 8.08 (dd, J = 8.6, 2.4 Hz, 1H, HzE), 8.04 (d, J = 1.8 Hz, 1H, HmE), 8.01–7.94 (m, 4H, HeE+eZ+tE+tZ), 7.92 (dd, J = 8.2, 2.4 Hz, 1H, HzZ), 7.91–7.86 (m, 5H, HcE+cZ+mZ+vE+vZ), 7.85 (d, J = 8.3 Hz, 1H, HaaZ), 7.71–7.53 (m, 17H, HdE+dZ+fE+fZ+iE+iZ+pE+pZ+qE+qZ+rE+uE+uZ+amE+amZ), 7.53–7.49 (m, 4H, HhE+hZ+lE+rZ), 7.47 (d, J = 1.8 Hz, 1H, HlZ), 7.42 (t, J = 8.0 Hz, 1H, HadE), 7.37 (t, J = 7.9 Hz, 1H, HadZ), 7.32–7.29 (m, 1H, HacE), 7.25 (t, J = 2.1 Hz, 1H, HabE), 7.22 (d, J = 7.7 Hz, 1H, HacZ), 7.15 (t, J = 2.0 Hz, 1H, HabZ), 6.97 (dd, J = 8.1, 2.4 Hz, 1H, HaeE), 6.92 (dd, J = 8.3, 2.4 Hz, 1H, HaeZ), 6.89–6.85 (m, 4H, HanE+anZ), 4.50 (q, J = 7.2 Hz, 2H, HxZ), 4.40 (q, J = 7.2 Hz, 2H, HxE), 4.16 (t, J = 6.0 Hz, 2H, HafE), 4.12 (t, J = 6.1 Hz, 2H, HafZ), 3.79–3.76 (m, 6H, HaoE+aoZ), 3.15 (t, J = 7.5 Hz, 4H, HajE+ajZ), 3.05 (t, J = 7.3 Hz, 4H, HaiE+aiZ), 2.96 (t, J = 7.1 Hz, 2H, HahE), 2.94 (t, J = 7.1 Hz, 1H, HahZ), 2.51 (s, 3H, HoE), 2.49 (d, J = 2.5 Hz, 6H, HgE+gZ), 2.45 (s, 3H, HoZ), 2.26–2.20 (m, 4H, HagE+agZ), 1.43 (t, J = 7.2 Hz, 3H, HwZ), 1.42 (t, J = 7.1 Hz, 3H, HwE). 13C NMR (151 MHz, CD2Cl2, ~7:3 ratio of E-S23:Z-S23, each isomer exists as a ~87:13 ratio of cis:trans acyl hydrazone rotamers, major rotamers reported) δ 192.8, 192.7, 173.13, 173.11, 166.2, 163.9, 161.9, 160.1, 160.0, 154.5, 151.5, 150.3, 150.0, 147.7, 146.1, 143.6 (2C), 142.24, 142.18, 142.06, 142.02, 141.7, 140.1, 140.0, 139.9, 139.6, 139.5, 139.4, 139.12, 139.07, 138.5, 138.4, 137.7, 137.6, 137.3, 137.0, 136.6, 136.02, 135.95 135.8, 135.6, 135.4, 135.0, 133.4 (4C), 132.3, 131.4 (2C), 131.1, 131.0, 130.8, 130.7, 130.2, 130.1 (2C), 129.93, 129.90, 129.7, 129.61, 129.56, 129.3 (2C), 129.15, 129.12 (2C), 129.09 (2C), 128.6, 128.5, 128.42 (2C), 128.40 (2C), 126.90, 126.86, 125.43, 125.40, 125.07, 125.02, 124.98, 123.4, 121.1, 120.8, 120.04, 119.96, 114.9, 114.7 (3C), 113.9, 113.7, 112.7, 112.2, 66.72, 66.69, 62.2, 61.7, 55.9 (2C), 35.7, 35.6, 33.92, 33.90, 33.4 (2C), 29.4, 29.3, 21.12, 21.07 (2C), 21.06, 14.8, 14.6. HRMS (NSI+): m/z = 1112.3949 [M+H]+ (calcd. 1112.3944 for C66H58DN6O7S2).
