M. Yan et al.
Journal of Photochemistry & Photobiology, A: Chemistry 416 (2021) 113325
Scheme 1. Synthetic routes of JY74 and JY75. Reaction conditions: (I) i: TBAF, THF; ii: 10, Pd2(dba)3, AsPh3, Et3N; (II) i: TBAF, THF; ii: 11, Pd2(dba)3, AsPh3, Et3N;
iii: 20 % NaOH (aq), THF/MeOH.
6.3 Hz, 18 H), 7.10 (d, J =7.7 Hz, 2 H), 7.01 – 6.92 (m, 12 H), 5.40 (d, J
=4.4 Hz, 4 H), 3.82 (t, J =6.3 Hz, 8 H), 1.45 (d, J =4.7 Hz, 18 H), 0.99 (q,
J =6.8 Hz, 8 H), 0.92 – 0.84 (m, 3 H), 0.75 (q, J =6.8 Hz, 8 H), 0.61 –
0.35 (m, 44 H). 13C NMR (101 MHz, chloroform-d) δ 159.83, 152.51,
151.52, 151.42, 150.68, 150.28, 145.66, 145.22, 143.52, 142.29,
138.13, 132.27, 132.15, 130.75, 130.23, 129.81, 127.56, 125.16,
125.12, 123.73, 123.59, 123.54, 123.38, 122.28, 122.24, 121.92,
120.68, 114.43, 109.94, 105.13, 99.63, 96.40, 68.56, 54.26, 53.66,
31.31, 29.71, 28.51, 28.47, 28.40, 25.08, 22.15, 19.13, 13.74, 11.96.
FT-IR (ATR): v = 3432, 3064, 3019, 2922, 2853, 2134, 1897, 1800,
1589, 1513, 1485, 1456, 1378, 1334, 1321, 1303, 1246, 1211, 1160,
1121, 1188, 1160, 1121, 1098, 1060, 999, 974, 919, 881, 838, 825, 795,
769, 742, 711, 673, 654, 627, 620, 573, 560, 532 and 480 cmꢀ 1. HR-MS
2 H), 7.01 – 6.90 (m, 12 H), 5.39 (d, J =3.2 Hz, 4 H), 3.83 (s, 8 H), 1.06 –
0.93 (m, 8 H), 0.77 (dt, J = 13.0, 6.2 Hz, 8 H), 0.66 – 0.40 (m, 44 H). 13C
NMR (101 MHz, chloroform-d) δ 178.77, 159.83, 152.08, 151.62,
151.43, 150.70, 150.48, 145.70, 145.23, 143.57, 142.71, 141.48,
139.03, 138.10, 135.82, 133.40, 132.38, 131.35, 130.42, 130.31,
129.92, 128.24, 127.58, 125.17, 125.12, 123.73, 123.58, 123.54,
123.38, 122.30, 122.23, 120.55, 114.85, 110.07, 106.97, 105.13, 98.26,
68.54, 54.28, 53.72, 31.36, 29.73, 28.59, 28.55, 28.43, 25.12, 22.23,
13.79. FT-IR (ATR): v = 3432, 3063, 3019, 2952, 2851, 2186, 1797,
1723, 1688, 1601, 1513, 1485, 1456, 1406, 1377, 1337, 1305, 1288,
1259, 1206, 1172, 1160, 1097, 1061, 997, 973, 920, 881, 856, 823, 794,
769, 741, 712, 671, 664, 627, 620, 559, 503 and 480 cmꢀ 1. HR-MS
+
(MALDI): m/z [M]
calcd for C125H121N5O6Zn, 1851.8608; found,
+
(MALDI): m/z [M] calcd for C127H137N5O4SiZn, 1887.9731; found,
1851.8613.
1887.9738.
2.2.4. Synthesis of compound JY75
2.2.3. Synthesis of compound JY74
The ester precursor of JY75 was prepared in 90 % yield using the
same method of JY74. Subsequently, 5 mL 20 % NaOH (aq.) was added
to the solution of ester precursors of JY75 (70 mg, 0.035 mmol) in THF
(10 mL) and MeOH (8 mL), and stirred at room temperature for over-
night. The mixture was extracted with DCM (3 × 100 mL), washed with
HCl (1 M aq.) and water (100 mL). The organic layer was dried over
anhydrous MgSO4 and concentrated under vacuum, and the residue was
purified by column chromatography using DCM/MeOH (20/1) to give
the product JY75 (62 mg, 85 %). M.P.: 147ꢀ 150 ◦C. 1H NMR (400 MHz,
chloroform-d) δ 10.03 (d, J =4.6 Hz, 2 H), 9.18 (d, J =4.6 Hz, 2 H), 8.97
(d, J =4.6 Hz, 2 H), 8.72 (d, J =4.6 Hz, 2 H), 8.31ꢀ 8.24 (m, 3 H), 8.21
(d, J =8.3 Hz, 2 H), 7.97 (d, J =7.3 Hz, 1 H), 7.66 (t, J =8.4 Hz, 2 H),
7.50 (s, 2 H), 7.41ꢀ 7.26 (m, 18 H), 7.09 (d, J =6.4 Hz, 2 H), 7.02ꢀ 6.89
(m, 12 H), 5.38 (d, J =4.5 Hz, 4 H), 3.84 (d, J =2.6 Hz, 8 H), 1.00 (dt, J
To a stirred solution of compound 9 (90 mg, 0.048 mmol) in THF
(10 mL) was added TBAF (0.24 mL, 1 M in THF) under nitrogen. After
stirring for 1 h at room temperature, the mixture was diluted with water
and extracted with DCM (3 × 100 mL). The organic layer was dried over
Na2SO4 and concentrated under vacuum. Then the obtained raw mate-
rial, 4-iodobenzoic acid (47.6 mg, 0.19 mmol), Pd2(dba)3 (13 mg,
0.014 mmol), and AsPh3 (29 mg, 0.096 mmol) were dissolved in a
mixture of THF (20 mL) and Et3N (5 mL) under nitrogen. The solution
was heated at reflux for 6 h. After being cooled down, the reaction
mixture was extracted with DCM (3 × 100 mL), the combined organic
layer was washed with HCl (1 M aq) and water (100 mL), concentrated
in vacuum. The residue was purified by column chromatography using
DCM/MeOH (25/1) to give the product JY74 (76 mg, 85 %). M.P.:
1
151ꢀ 154 C. H NMR (400 MHz, chloroform-d) δ 9.69 (d, J =4.4 Hz,
2 H), 9.19 (d, J =4.5 Hz, 2 H), 8.91 (d, J =4.3 Hz, 2 H), 8.72 (d, J
=4.4 Hz, 2 H), 8.26 (s, 2 H), 8.10 (d, J =7.5 Hz, 2 H), 7.65 (t, J =8.0 Hz,
2 H), 7.51 (s, 2 H), 7.32 (dd, J = 18.6, 8.3 Hz, 18 H), 7.10 (d, J =7.4 Hz,
=6.6 Hz, 8 H), 0.74 (dt, J = 14.5, 6.1 Hz, 8 H), 0.64ꢀ 0.37 (m, 44 H). 13
C
◦
NMR (101 MHz, chloroform-d) δ 170.75, 159.86, 156.17, 156.14,
153.25, 153.23, 152.47, 152.44, 151.53, 151.44, 150.76, 150.52,
145.70, 145.23, 145.20, 143.58, 143.55, 142.47, 138.08, 133.40,
3