Compound Z-2-left
Ethyl (5Z,19E)-33-(3'-formyl-3-methyl-[1,1'-biphenyl]-4-yl)-23-methyl-17-oxo-9-oxa-13,14-dithia-4,5,18,19-tetraaza-3(6,8)-quinolina-7(2,5)-pyridina-1,8(1,3),2(1,4)-tribenzenacycloicosaphane-5,19-diene-6-carboxylate-20-d
From: Pick-up, transport and release of a molecular cargo using a small-molecule robotic arm
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InChIKey QSBSAOASRDKMJY-BPKLSFAISA-N
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
A solution of S23 (45 mg, 40.45 µmol, 1.0 eq) and trifluoroacetic acid (9.0 µL, 0.12 mmol, 3.0 eq) in CHCl3 (16 mL, 2.5 mM) was stirred at r. t. for 48 h. Triethylamine (34 µL) was added and the solution was extracted with saturated sodium bicarbonate solution (20 mL). The aqueous phase was separated and extracted with CH2Cl2 (2 × 20 mL). The combined organics were dried (Na2SO4) and concentrated under reduced pressure to give a dark brown oil. Flash column chromatography (SiO2, EtOAc/CH2Cl2 (0.2% Et3N), 0% → 5%) gave the desired product as a yellow solid (23 mg, 23.06 mmol, 57%). Mp >220 °C (dec.) 1H NMR (600 MHz, CD2Cl2, 85:15 ratio of cis:trans acyl hydrazone rotamers, major rotamer reported) δ 13.39 (s, 1H, Hn), 10.12 (s, 1H, Ha), 8.98 (d, J = 2.2 Hz, 1H, Hj), 8.87 (d, J = 1.7 Hz, 1H, Hy), 8.65 (s, 1H, Hak), 8.23–8.20 (m, 3H, Hb+k+s), 8.01–7.96 (m, 2H, He+z), 7.94 (d, J = 1.8 Hz, 1H, Hm), 7.90 (dt, J = 7.8, 1.4 Hz, 1H, Hc), 7.87 (d, J = 8.1 Hz, 1H, Haa), 7.72–7.64 (m, 4H, Hd+f+i+t), 7.59 (s, 1H, Hp), 7.55 (dd, J = 7.8, 2.0 Hz, 1H, Hq), 7.54–7.49 (m, 3H, Hh+r+u), 7.48 (d, J = 1.7 Hz, 1H, Hl), 7.40 (t, J = 7.9 Hz, 1H, Had), 7.36 (dt, J = 7.6, 1.3 Hz, 1H, Hv), 7.29 (d, J = 7.6 Hz, 1H, Hac) 7.20 (t, J = 2.0 Hz, 1H, Hab), 6.96 (dd, J = 8.0, 1.8, 1H, HaE), 4.51 (q, J = 7.1 Hz, 2H, Hx), 4.22 (t, J = 6.0 Hz, 2H, Haf), 3.21 (t, J = 6.8 Hz, 2H, Haj), 3.09 (t, J = 6.9 Hz, 2H, Hai), 2.94 (t, J = 6.7 Hz, 2H, Hah), 2.49 (s, 3H, Hg), 2.46 (s, 3H, Ho), 2.21 (p, J = 6.3 Hz, 2H, Hag), 1.44 (t, J = 7.2 Hz, 3H, Hw). Selected peaks for the minor rotamer: 13.24 (s, 1H, Hn), 4.15 (t, J = 6.0 Hz, 2H, Haf), 3.18 (t, J = 6.8 Hz, 2H, Haj), 2.70 (t, J = 6.6 Hz, 1H, Hai). 1H NMR (600 MHz, C2D2Cl4, 85:15 ratio of cis:trans acyl hydrazone rotamers, major rotamer reported) δ 13.35 (s, 1H, Hn), 10.12 (s, 1H, Ha), 9.02 (d, J = 2.1 Hz, 1H, HJ), 8.89 (d, J = 1.4 Hz, 1H, Hy), 8.85 (s, 1H, Hn), 8.22 (s, 1H, Hs), 8.22–8.19 (m, 2H, Hb+k), 8.02–7.96 (m, 3H, He+m+z), 7.92 (d, J = 7.5 Hz, 1H, Hc), 7.85 (d, J = 8.1 Hz, 1H, Haa), 7.71–7.67 (m, 3H, Hd+f+i), 7.66 (d, J = 7.9 Hz, 1H, Ht), 7.59 (s, 1H, Hp), 7.58–7.51 (m, 4H, Hh+q+r+u), 7.49 (s, 1H, Hl), 7.43 (t, J = 7.9 Hz, 1H, Hz), 7.37 (d, J = 7.5 Hz, 1H, Hv), 7.29 (d, J = 7.7 Hz, 1H, Hac), 7.20 (m, 1H, Hab), 6.98 (dd, J = 8.5, 2.5 Hz, 1H, HaE), 4.54 (q, J = 7.0 Hz, 2H, Hx), 4.21 (t, J = 5.9 Hz, 2H, Haf), 3.23 (t, J = 6.8 Hz, 2H, Haj), 3.11 (t, J = 6.7 Hz, 2H, Hai), 2.96 (t, J = 6.8 Hz, 2H, Hah), 2.51 (s, 3H, Hg), 2.48 (s, 3H, Ho), 2.22 (p, J = 6.3 Hz, 2H, Hag), 1.51 (t, J = 7.0 Hz, 3H, Hw). Selected peaks for the minor rotamer: 13.13 (s, 1H, Hn), 4.15 (t, J = 5.9 Hz, 2H, Haf), 3.19 (t, J = 6.8 Hz, 2H, Haj), 2.99 (t, J = 7.6 Hz, 2H, Hah), 2.71 (t, J = 6.8 Hz, 1H, Hai), 2.32–2.24 (m, 2H, Hag). 13C NMR (151 MHz, C2D2Cl4, 85:15 ratio of cis:trans acyl hydrazone rotamers, major rotamer reported) δ 192.5, 172.9, 162.8, 159.2, 153.8, 149.5, 147.0, 143.7, 141.7, 141.2, 141.0, 140.9, 140.0, 139.3, 138.8, 138.4, 137.7, 136.7, 136.6, 136.2, 135.4, 135.3, 135.1, 134.8, 134.6, 133.6, 133.0, 130.9, 130.6, 130.3, 130.2, 129.8, 129.6, 129.4, 129.3, 129.1, 129.0, 128.9, 127.9, 127.7, 124.9 (2C), 123.6, 122.7, 120.6, 120.2, 119.3, 115.4, 113.3, 111.9, 66.2, 61.6, 35.2, 33.7, 32.6, 28.1, 20.8, 20.7, 14.2. HRMS (NSI+): m/z = 976.3424 [M+H]+ (calcd. 976.3420 for C58H50DN6O5S2).
