5.2 Experimental data for Chapter 2
5.2.2 Synthetic procedures and characterisation for coupling products
5.2.2.1 Arylation of benzyl potassium trifluoroborates
GP(II): A 5 mL microwave vial equipped with a magnetic stir bar was charged with the
cyanoarene (0.15 mmol, 1.0 equiv.), the potassium benzyltrifluoroborate salt (0.18 mmol, 1.2 equiv.) and the photoredox catalyst [Ir(dF(CF3)ppy)2(dtbpy)]PF6 (Ir-3, 0.9 mg,
0.5 mol%). The vial was sealed and evacuated/backfilled with argon three times. Then 2.5 mL of degassed acetone was added through the septum to obtain a clear yellow transparent 0.06 M solution. The vial was then irradiated for the indicated time with
Thorlab blue LEDs generating about 35°C temperature. The crude mixture was then concentrated in vacuo and the residue purified by flash column chromatography on silica gel (Et2O/EtOAc/hexane/Et3N, 1:1:2:0.04) to yield the pure product.
4-benzylpyridine (161)
161 was obtained following GP(II) as a colourless oil (21 mg, 0.12 mmol) in 81% yield
after 48 h of irradiation. 1H-NMR (600 MHz, CDCl
3) δ 8.53 (br s, 2H, H1), 7.33 (t, J =
7.5 Hz, 2H, H7), 7.26 (t, J = 7.4 Hz, 1H, H8), 7.18 (d, J = 7.4 Hz, 2H, H6), 7.15 (d, J = 4.4
Hz, 2H, H2), 3.99 (s, 2H, H4). 13C-NMR (151 MHz, CDCl3) δ 150.6 (C1), 149.3 (C3),
138.7 (C5), 129.0 (C6), 128.8 (C7), 126.7 (C8), 124.4 (C2), 41.3 (C4). HRMS for
[C12H12N]+ calculated 170.0970 found 170.0977. Rf (1:1 EtOAc/hexane) = 0.12.
Experimental 132
4-(4-methoxybenzyl)pyridine (162)
162 was obtained following GP(II) as a colourless oil (22 mg, 0.11 mmol) in 76% yield
after 16 h of irradiation. 1H-NMR (600 MHz, CDCl
3) δ 8.49 (d, J = 5.8 Hz, 2H, H1),
7.13 – 7.07 (m, 4H, H2 and H6), 6.86 (d, J = 8.7 Hz, 2H, H7), 3.91 (2H, s, H4), 3.80 (s,
3H, H9). 13C-NMR (151 MHz, CDCl3) δ 158.4 (C8), 150.6 (C3), 149.7 (C1), 130.9 (C5),
130.0 (C2), 124.1 (C6), 114.1 (C7), 55.3 (C9), 40.3 (C4). HRMS for [C13H14NO]+
calculated 200.1075 found 200.1078. Rf (1:1 EtOAc/hexane) = 0.13. Spectroscopic data
were consistent with literature values.[271]
4-(1-(3-methoxyphenyl)-2-methylpropyl)pyridine (163)
163 was obtained following GP(II) as a yellowish solid (33 mg, 0.14 mmol) in 86% yield
after 3 h of irradiation. Also obtained using 168 as starting material in 43% yield. 1H- NMR (600 MHz, CDCl3) δ 8.47 (d, J = 5.1 Hz, 2H, H14), 7.23 – 7.18 (m, 3H, H13 and H7 ), 6.86 (br d, J = 7.7 Hz, 1H, H6), 6.82 – 6.80 (m, 1H, H10), 6.73 (dd, J = 8.2, 2.5, 1H, H8), 3.78 (s, 3H, H11), 3.36 (d, J = 10.8 Hz, 1H, H4), 2.47 (dsept, J = 10.8, 6.6 Hz, 1H, H3), 0.90 (d, J = 6.5 Hz, 3H, H1 or H2), 0.87 (d, J = 6.5 Hz, 3H, H1 or H2). 13C-NMR (151 MHz, CDCl3) δ 159.7 (C9), 153.6 (C5), 149.8 (C14), 144.6 (C12), 129.6 (C7), 123.4 (C6), 120.4 (C13), 114.4 (C10), 111.2 (C8), 60.2 (C4), 55.1 (C11), 31.4 (C3), 21.6 (C1 or C2), 21.5 (C1 or C2). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2988, 2972, 2902, 1592, 1557, 1484, 1466, 1452, 1438, 1408, 1393, 1385, 1277, 1260, 1242, 1232, 1148, 1066, 1048, 889, 880, 833, 820, 780, 761, 737, 700. HRMS for [C16H20NO]+ calculated 242.1545 found 242.1549. Rf (1:1 EtOAc/hexane) = 0.16. M.p. = 47–49°C.
Experimental 133
4-(4-methoxybenzyl)benzonitrile (173)
173 was obtained following GP(II) as a colourless oil (14 mg, 0.065 mmol) in 43% yield
after 16 h of irradiation. 1H-NMR (600 MHz, CDCl
3) δ 7.57 (d, J = 8.2 Hz, 2H, H3),
7.28 (d, J = 8.3 Hz, 2H, H4), 7.08 (d, J = 8.5 Hz, 2H, H8), 6.86 (d, J = 8.6 Hz, 2H, H9),
3.98 (s, 2H, H6), 3.80 (s, 3H, H11). 13C-NMR (151 MHz, CDCl3) δ 158.4 (C10), 147.2
(C7), 132.3 (C5), 131.4 (C3), 129.9 (C4), 129.5 (C8), 119.0 (C1), 114.2 (C9), 109.9 (C2),
55.3 (C4), 41.1 (C6). HRMS for [C15H14NO]+ calculated 224.1075 found 224.1072. Rf
(1:1 EtOAc/hexane) = 0.51. Spectroscopic data were consistent with literature values.[271]
2-(4-methoxybenzyl)pyrimidine (171)
171 was obtained following GP(II) as a colourless oil (8.5 mg, 0.042 mmol) in 28% yield
after 72 h of irradiation. 1H-NMR (600 MHz, CDCl 3) δ 8.68 (d, J = 4.9 Hz, 2H, H2), 7.29 (d, J = 8.6 Hz, 2H, H6), 7.12 (t, J = 4.9 Hz, 1H, H1), 6.86 (d, J = 8.7 Hz, 2H, H7), 4.24 (s, 2H, H4), 3.78 (s, 3H, H9). 13C-NMR (151 MHz, CDCl3) δ 170.4 (C3), 158.3 (C8), 157.3 (C2), 130.3 (C5), 130.1 (C6), 118.6 (C1), 114.0 (C7), 55.2 (C9), 45.2 (C4) IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2988, 2972, 2902, 1611, 1571, 1561, 1511, 1415, 1394, 1382, 1301, 1248, 1178, 1076, 1066, 1056, 892, 879, 809. HRMS for [C12H13N2O]+ calculated 201.1028 found 201.1028. Rf (1:1 EtOAc/hexane) = 0.09.
Experimental 134
5.2.2.2 Arylation of boronic esters with cyanoarenes in flow
GP(III): A 5 mL conical shape microwave vial was charged with the cyanoarene
(0.25 mmol, 1.0 equiv.), the benzyl pinacol boronic ester (0.30 mmol, 1.2 equiv), and the photoredox catalyst [Ir(dF(CF3)ppy)2(dtbpy)]PF6 (Ir-3, 3.0 mg, 1.0 mol%). Then 1.0 mL
of acetone was added to obtain a clear yellow transparent 0.25 M solution after sonication for 1 min. The clear yellow solution was then pumped at 100 µL/min through a Vapourtec UV-150 photochemical reactor (10 mL reactor coil, FEP tubing, τ = 100 min) held at 60°C. Once the reaction mixture has fully be taken up by the pump, the input was swapped to acetone solvent to push the rest of the reaction mixture through the reactor. When the reaction plug was exiting the output stream (yellow to orange colour), the totality of the plug was collected in a vial wrapped in aluminium foil and concentrated in
vacuo. The residue was then purified by Bioatage flash column chromatography on KP-
NH modified silica gel cartridge (0% to 20% EtOAc in hexane gradient) to yield the pure product.
4-(4-methoxybenzyl)pyridine (162)
162 was obtained following GP(III) as a pale yellow oil (40 mg, 0.20 mmol) in 81%
yield. 1H-NMR (600 MHz, CDCl
3) δ 8.49 (d, J = 5.8 Hz, 2H, H1), 7.13 – 7.07 (m, 4H,
H2 and H6), 6.86 (d, J = 8.7 Hz, 2H, H7), 3.91 (2H, s, H4), 3.80 (s, 3H, H9). 13C-NMR
(151 MHz, CDCl3) δ 158.4 (C8), 150.6 (C3), 149.7 (C1), 130.9 (C5), 130.0 (C2), 124.1
(C6), 114.1 (C7), 55.3 (C9), 40.3 (C4). HRMS for [C13H14NO]+ calculated 200.1075
found 200.1078. Rf (1:1 EtOAc/hexane) = 0.13. Spectroscopic data were consistent with
Experimental 135
4-(4-methylbenzyl)pyridine (191)
191 was obtained following GP(III) as a colourless oil (32 mg, 0.17 mmol) in 70% yield.
1H-NMR (600 MHz, CDCl
3) δ 8.49 (d, J = 5.3 Hz, 2H, H1), 7.13 (d, J = 7.8 Hz, 2H, H7),
7.10 (d, J = 5.5 Hz, 2H, H2), 7.07 (d, J = 7.8 Hz, 2H, H6), 3.93 (s, 2H, H4), 2.34 (s, 3H,
H9).13C-NMR (151 MHz, CDCl3) δ 150.3 (C3), 149.8 (C1), 136.3 (C5), 135.8 (C8), 129.4
(C7), 128.9 (C6), 124.1 (C2), 40.8 (C4), 21.0 (C9). HRMS for [C13H14N]+ calculated
184.1121 found 184.117. Rf (1:1 EtOAc/hexane) = 0.13. Spectroscopic data were
consistent with literature values.[272]
4-(benzyl)pyridine (161)
161 was obtained following GP(III) as a colourless oil (28 mg, 0.16 mmol) in 66% yield.
1H-NMR (600 MHz, CDCl3) δ 8.53 (br s, 2H, H
1), 7.33 (t, J = 7.5 Hz, 2H, H7), 7.26 (t, J
= 7.4 Hz, 1H, H8), 7.18 (d, J = 7.4 Hz, 2H, H6), 7.15 (d, J = 4.4 Hz, 2H, H2), 3.99 (s, 2H,
H4). 13C-NMR (151 MHz, CDCl3) δ 150.6 (C1), 149.3 (C3), 138.7 (C5), 129.0 (C6), 128.8
(C7), 126.7 (C8), 124.4 (C2), 41.3 (C4). HRMS for [C12H12N]+ calculated 170.0970 found
170.0977. Rf (1:1 EtOAc/hexane) = 0.13. Spectroscopic data were consistent with
literature values.[207]
4-(1-(4-methoxyphenyl)ethyl)pyridine (192)
192 was obtained following GP(III) as a colourless oil (44 mg, 0.21 mmol) in 83% yield.
1H-NMR (600 MHz, CDCl
3) δ 8.49 (d, J = 5.9 Hz, 2H), 7.16 – 7.05 (m, 4H, H6 and H2),
6.85 (d, J = 8.6 Hz, 2H, H7), 4.07 (q, J = 7.2 Hz, 1H, H4), 3.79 (s, 3H, H9), 1.61 (d, J =
7.2 Hz, 3H, H10). 13C-NMR (151 MHz, CDCl3) δ 158.3 (C8), 155.5 (C3), 149.8 (C2),
Experimental 136
[C12H12N]+ calculated 214.1226 found 214.1220. Rf (1:1 EtOAc/hexane) = 0.12.
Spectroscopic data were consistent with literature values.[273]
1-(4-methoxybenzyl)isoquinoline (184)
184 was obtained following GP(III) as a pale green oil (47 mg, 0.19 mmol) in 75% yield.
1H-NMR (600 MHz, CDCl 3) δ 8.50 (d, J = 5.7 Hz, 1H, H2), 8.17 (d, J = 8.5 Hz, 1H, H8), 7.81 (d, J = 8.2 Hz, 1H, H5), 7.64 (ddd, J = 8.1, 7.0, 1.0 Hz, 1H, H6), 7.56 (d, J = 5.7 Hz, 1H, H3), 7.53 (ddd, J = 8.5, 6.9, 1.1 Hz, 1H, H7), 7.21 (d, J = 8.7 Hz, 2H, H12), 6.80 (d, J = 8.7 Hz, 2H, H13), 4.62 (s, 2H, H10), 3.75 (s, 3H, H15). 13C-NMR (151 MHz, CDCl3) δ 160.5 (C1), 158.0 (C14), 142.0 (C2), 136.6 (C4), 131.6 (C11), 129.8 (C7), 129.5 (C12), 127.3 (C6), 127.1 (C5), 127.0 (C9), 125.8 (C8), 119.7 (C3), 113.9 (C13), 55.2 (C15), 41.2 (C10).
HRMS for [C17H16ON]+ calculated 250.1226 found 250.1216. Rf (1:1 EtOAc/hexane) =
0.48. Spectroscopic data were consistent with literature values.[274]
1-(1-phenylethyl)isoquinoline (194)
194 was obtained following GP(III) as a white solid (44 mg, 0.19 mmol) in 75% yield.
1H-NMR (600 MHz, CDCl 3) δ 8.59 (d, J = 5.7 Hz, 1H, H2), 8.19 (d, J = 8.6 Hz, 1H, H8), 7.79 (d, J = 8.2 Hz, 1H, H5), 7.60 (t, J = 7.5 Hz, 1H, H6), 7.55 (d, J = 5.7 Hz, 1H, H7), 7.49 (t, J = 7.8 Hz, 1H, H3), 7.33 (d, J = 7.5 Hz, 2H, H13), 7.26 (t, J = 7.6 Hz, 2H, H14), 7.16 (t, J = 7.3 Hz, 1H, H15), 5.10 (q, J = 7.0 Hz, 1H, H10), 1.87 (d, J = 7.0 Hz, 3H, H11). 13C-NMR (151 MHz, CDCl 3) δ 162.9 (C1), 145.9 (C2), 141.7 (C12), 136.5 (C4), 129.5 (C6), 128.5 (C14), 127.6 (C13), 127.4 (C8), 127.0 (C7), 126.2 (C15), 125.3 (C5), 120.0 (C3), 43.2 (C10), 21.9 (C11). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3060, 3020, 2968, 2925, 1619, 1584,
1560, 1491, 1354, 1140, 876. HRMS for [C17H16N]+ calculated 234.1277 found
Experimental 137
1-(4-methylbenzyl)isoquinoline (193)
193 was obtained following GP(III) as a colourless oil (43 mg, 0.18 mmol) in 74% yield.
1H-NMR (600 MHz, CDCl 3) δ 8.51 (d, J = 5.7 Hz, 1H, H2), 8.17 (d, J = 8.5 Hz, 1H, H8), 7.81 (d, J = 8.2 Hz, 1H, H5), 7.63 (t, J = 7.5 Hz, 1H, H6), 7.56 (d, J = 5.7 Hz, 1H, H3), 7.53 (t, J = 7.6 Hz, 1H, H7), 7.19 (d, J = 7.9 Hz, 2H, H12), 7.07 (d, J = 7.9 Hz, 2H, H13), 4.65 (s, 2H, H10), 2.29 (s, 3H, H15). 13C-NMR (151 MHz, CDCl3) δ 160.4 (C1), 142.0 (C2), 136.6 (C14), 136.4 (C4), 135.7 (C11), 129.8 (C7), 129.2 (C13), 128.5 (C12), 127.3 (C9), 127.2 (C5), 125.9 (C8), 119.7 (C3), 41.7 (C10), 21.0 (C15). HRMS for [C17H16N]+
calculated 234.1277 found 234.1265. Rf (1:1 EtOAc/hexane) = 0.34. Spectroscopic data
were consistent with literature values.[275]
1-benzhydrylisoquinoline (195)
195 was obtained following GP(III) as a white solid (62 mg, 0.21 mmol) in 84% yield.
1H-NMR (600 MHz, CDCl 3) δ 8.56 (d, J = 5.7 Hz, 1H, H2), 8.27 (d, J = 8.6 Hz, 1H, H8), 7.85 (d, J = 8.2 Hz, 1H, H5), 7.66 (t, J = 7.5 Hz, 1H, H6), 7.57 – 7.54 (m, 2H, H7 and H3), 7.34 – 7.31 (m, 4H, H13), 7.29 – 7.23 (m, 6H, H12 and H14), 6.52 (s, 1H, H10). 13C-NMR (151 MHz, CDCl3) δ 161.9 (C1), 142.8 (C11), 142.0 (C2), 136.6 (C4), 129.6 (C6), 128.3 (C13), 127.5 (C12), 127.3 (C8 and C9), 126.5 (C7), 125.2 (C14), 119.6 (C5), 54.8 (C10). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3056, 3020, 1621, 1586, 1560, 1495, 1447, 1380, 1344, 1156,
1029, 826. HRMS for [C22H18N]+ calculated 296.1434 found 296.1421. Rf (1:9
Experimental 138
1-(4-fluorobenzyl)isoquinoline (196)
196 was obtained following GP(III) as an amorphous white solid (39 mg, 0.16 mmol) in
65% yield. 1H-NMR (600 MHz, CDCl 3) δ 8.50 (d, J = 5.6 Hz, 1H, H2), 8.13 (d, J = 8.4 Hz, 1H, H8), 7.83 (d, J = 8.1 Hz, 1H, H5), 7.65 (t, J = 7.5 Hz, 1H, H6), 7.58 (d, J = 5.7 Hz, 1H, H3), 7.55 (t, J = 7.6 Hz, 1H, H7), 7.26 – 7.22 (m, 2H, H12), 6.95 (t, J = 8.5 Hz, 2H, H13), 4.65 (s, 2H, H10). 13C-NMR (151 MHz, CDCl3) δ 161.4. (d, J = 244 Hz, C14), 159.9 (C1), 142.0 (C2), 136.6 (C4), 135.0 (d, J = 3.2 Hz, (C11), 129.9 (d, J = 4.6 Hz, C12), 127.4 (C5), 127.3 (C6), 127.1 (C9), 125.6 (C8), 119.9 (C3), 115.3 (d, J = 21 Hz, C13), 41.1 (C10).
HRMS for [C16H13NF]+ calculated 238.1027 found 238.1025. Rf (1:1 EtOAc/hexane) =
0.48. Spectroscopic data were consistent with literature values.[276]
1-(3,5-bis(trifluoromethyl)benzyl)isoquinoline (197)
197 was obtained following GP(III) as a white solid (48 mg, 0.13 mmol) in 55% yield.
1H-NMR (600 MHz, CDCl 3) δ 8.52 (d, J = 5.7 Hz, 1H, H2), 8.10 (d, J = 8.5 Hz, 1H, H8), 7.87 (d, J = 8.2 Hz, 1H, H5), 7.78 (s, 2H, H12), 7.73 (s, 1H, H14), 7.70 (t, J = 7.5 Hz, 1H, H6), 7.63-7.60 (m, 2H, H7 and H3), 4.78 (s, 2H, H10).13C-NMR (151 MHz, CDCl3) δ 157.9 (C1), 142.2 (C2), 141.6 (C11), 136.6 (C4), 131.6 (q, J = 33.2 Hz, C13), 130.2 (C6), 129.0 (q, J = 3.6 Hz, C12), 127.7 (C5 and C7), 126.9 (C9), 124.8 (C8), 123.3 (q, J = 273 Hz,
C15) 120.5 (sept, J = , 3.8 Hz, C14), 120.4 (C3), 41.0 (C10). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) =
3051, 2929, 1621, 1586, 1558, 1506, 1463, 1372, 1280, 1165, 1116, 880, 828. HRMS for
[C18H12NF6]+ calculated 356.0868 found 356.0858. Rf (1:1 EtOAc/hexane) = 0.67. M.p.
Experimental 139
1-(2,6-difluorobenzyl)isoquinoline (198)
198 was obtained following GP(III) as a white solid (40 mg, 0.16 mmol) in 63% yield. 1H-NMR (600 MHz, CDCl3) δ 8.42 (d, J = 5.7 Hz, 1H, H 2), 8.30 (d, J = 8.4 Hz, 1H, H8), 7.85 (d, J = 8.1 Hz, 1H, H5), 7.73 – 7.68 (m, 1H, H6), 7.64 (t, J = 7.6 Hz, 1H, H7), 7.54 (d, J = 5.7 Hz, 1H, H3), 7.27 – 7.20 (m, 1H, H14), 6.94 (t, J = 7.8 Hz, 2H, H13), 4.73 (s, 2H, H10). 13C-NMR (151 MHz, CDCl3) δ 161.7 (dd, J = 248 Hz, J = 8.7 Hz, C12), 157.6 (C1), 142.0 (C2), 136.2 (C4), 129.8 (C6), 128.2 (t, J = 10.3 Hz, C14), 127.4 (C8), 127.2 (C9), 126.9 (C7), 124.8 (C5), 119.6 (C3), 114.8 (t, J = 19.9 Hz, C11), 111.1 (dd, J = 20.9, 5.1 Hz, C13), 28.4 (C10). 19F-NMR (376 MHz, CDCl3) δ -113.81. IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2924, 2853, 1623, 1590, 1566, 1465, 1380, 1205, 1019, 1003, 860, 743. HRMS for
[C16H12NF2]+ calculated 256.0932 found 256.0927. Rf (1:1 EtOAc/hexane) = 0.67. M.p.
83–85°C.
1-(3,5-dimethoxybenzyl)isoquinoline (199)
199 was obtained following GP(III) as a pale green oil (46 mg, 0.16 mmol) in 66% yield. 1H-NMR (600 MHz, CDCl3) δ 8.51 (d, J = 5.7 Hz, 1H, H 2), 8.17 (d, J = 8.5 Hz, 1H, H8), 7.82 (d, J = 8.2 Hz, 1H, H5), 7.65 (t, J = 7.5 Hz, 1H, H6), 7.58 (d, J = 5.7 Hz, 1H, H3), 7.54 (t, J = 7.6 Hz, 1H, H7), 6.46 (s, 2H, H12), 6.30 (s, 1H, H14), 4.62 (s, 2H, H10), 3.73 (s, 6H, H15). 13C-NMR (151 MHz, CDCl3) δ 160.8 (C13), 159.8 (C1), 141.9 (C2), 141.8 (C11), 136.6 (C4), 129.9 (C6), 127.3 (C9 and C8), 127.2 (C7), 125.8 (C5), 119.9 (C3), 106.9 (C12), 98.1 (C14), 55.2 (C15), 42.3 (C10). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3056, 3000, 2937, 2837, 1596, 1560, 1500, 1461, 1427, 1383, 1342, 1322, 1288, 1205, 1154, 1058, 822, 789, 747, 730, 684. HRMS for [C18H18NO2]+ calculated 280.1332 found 280.1328. Rf
Experimental 140
4-(4-methoxybenzyl)-1H-pyrrolo[2,3-b]pyridine (183)
183 was obtained following GP(III) (using 3.5 mL of acetone instead of 1.0 mL because
of the low starting material solubility) as a brownish solid (36 mg, 0.15 mmol) in 60% yield. 1H-NMR (600 MHz, CDCl 3) δ 11.12 (s, 1H, H1), 8.25 (d, J = 4.8 Hz, 1H, H6), 7.32 (d, J = 3.0 Hz, 1H, H2), 7.18 (d, J = 8.4 Hz, 2H, H11), 6.87 – 6.84 (m, 3H, H12 and H5), 6.51 (d, J = 3.3 Hz, 1H, H3), 4.23 (s, 2H, H9), 3.79 (s, 3H, H14). 13C-NMR (151 MHz, CDCl3) δ 158.2 (C13), 148.7 (C7), 143.4 (C6), 142.6 (C4), 131.4 (C10), 130.0 (C11), 124.6 (C2), 120.2 (C8), 116.0 (C5), 114.0 (C12), 99.3 (C3), 55.2 (C14), 38.2 (C9). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3127, 3000, 2929, 2837, 2762, 1592, 1508, 1439, 1348, 1243, 1181,
1031, 823. HRMS for [C15H15ON2]+ calculated 239.1179 found 239.1179. Rf (1:1
EtOAc/hexane) = 0.19. M.p. 116–118°C.
4-(4-methoxybenzyl)quinoline (184)
184 was obtained following GP(III) as a white solid (41 mg, 0.16 mmol) in 66% yield. 1H-NMR (600 MHz, CDCl3) δ 8.84 (d, J = 4.5 Hz, 1H, H 1), 8.12 (d, J = 7.6 Hz, 1H, H11), 8.07 (d, J = 7.6 Hz, 1H, H14), 7.73 (t, J = 7.6, 1H, H13), 7.56 (t, J = 7.6, 1H, H12), 7.17-7.10 (m, 3H, H6 and H2), 6.87 (d, J = 8.65 Hz, 2H, H7), 4.41 (s, 2H, H4), 3.81 (s, 3H, H9). 13C-NMR (151 MHz, CDCl3) δ 158.7 (C8), 150.1 (C15), 148.1 (C1), 147.3 (C3), 130.5 (C5), 130.0 (C13), 129.9 (C14), 129.2 (C6), 127.6 (C10), 126.6 (C12), 123.9 (C11),
121.7 (C2), 114.2 (C7), 55.3 (C9), 44.3 (C4). HRMS for [C17H16NO]+ calculated
250.1226 found 250.1227. Rf (1:1 EtOAc/hexane) = 0.75. M.p. 79–81°C. Spectroscopic
Experimental 141
4-(4-methoxybenzyl)picolinonitrile (181)
181 was obtained following GP(III) as a pale yellow oil (25 mg, 0.11 mmol) in 44%
yield. 1H-NMR (600 MHz, CDCl3) δ 8.72 (d, J = 5.0 Hz, 1H, H 1), 7.34 (d, J = 5.0 Hz, 1H, H2), 7.30 (s, 1H, H4), 7.17 (d, J = 8.5 Hz, 2H, H9), 6.88 (d, J = 8.6 Hz, 2H, H10), 4.16 (s, 2H, H7), 3.81 (s, 3H, H12). 13C-NMR (151 MHz, CDCl3) δ 163.3 (C11), 158.6 (C3), 150.2 (C1), 130.2 (C9), 129.9 (C5), 124.5 (C2), 122.6 (C8), 120.8 (C4), 116.6 (C6), 114.3 (C10), 55.3 (C12), 43.6 (C7). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2956, 2933, 2238, 1609, 1594, 1508, 1461, 1395, 1302, 1243, 1177, 1033, 830, 817, 775. HRMS for
[C14H13N2O]+calculated 225.1022 found 225.1023. Rf (1:1 EtOAc/hexane) = 0.54.
4-(4-methoxybenzyl)nicotinonitrile (182)
182 was obtained following GP(III) as a colourless oil (36 mg, 0.16 mmol) in 65% yield. 1H-NMR (600 MHz, CDCl3) δ 8.82 (s, 1H, H
1), 8.65 (d, J = 5.2 Hz, 1H, H5), 7.17 (d, J =
5.2 Hz, 1H, H4), 7.15 (d, J = 8.7 Hz, 2H, H9), 6.88 (d, J = 8.7 Hz, 2H, H10), 4.14 (s, 2H,
H7), 3.81 (s, 3H, H12).13C-NMR (151 MHz, CDCl3) δ 158.8 (C11), 154.1 (C3), 153.0 (C5),
152.8 (C1), 130.2 (C9), 128.6 (C8), 124.1 (C4), 116.0 (C6), 114.4 (C2), 110.3 (C10), 55.3
(C12), 38.9 (C7). HRMS for [C14H13ON2]+ calculated 225.1022 found 225.1019. Rf (1:1
Experimental 142
2-(4-methoxybenzyl)pyridine (170)
170 was obtained following GP(III) as a pale yellow oil (20 mg, 0.10 mmol) in 40%
yield. 1H-NMR (600 MHz, CDCl3) δ 8.55 (d, J = 4.5 Hz, 1H, H
1), 7.58 (td, J = 7.7,
1.2 Hz, 1H, H3), 7.19 (d, J = 8.5 Hz, 2H, H8), 7.11 (t, J = 8.2 Hz, 2H, H2 and H4), 6.85 (d,
J = 8.5 Hz, 2H, H9), 4.11 (s, 2H, H6), 3.79 (s, 3H, H11). 13C-NMR (151 MHz, CDCl3) δ
161.3 (C10), 158.2 (C5), 149.2 (C2), 136.6 (C3), 131.5 (C7), 130.1 (C8), 123.0 (C4), 121.2
(C2), 114.0 (C9), 55.2 (C11), 43.7 (C6). HRMS for [C13H14ON]+ 200.1070 found
200.1071. Rf (1:1 EtOAc/hexane) = 0.36. Spectroscopic data were consistent with
literature values.[277]
2-benzhydrylquinoline (185)
185 was obtained following GP(III) as a colourless oil (41 mg, 0.14 mmol) in 55% yield.
1H-NMR (400 MHz, CDCl 3) δ 8.08 (t, J = 7.8 Hz, 2H, H7 and H2), 7.79 (dd, J = 8.1, 1.1 Hz, 1H, H5), 7.70 (ddd, J = 8.5, 6.9, 1.4 Hz, 1H, H3), 7.51 (ddd, J = 8.1, 7.0, 1.1 Hz, 1H, H4), 7.33 – 7.27 (m, 5H, H8 and H12), 7.26 – 7.21 (m, 6H, H13 and H14), 5.94 (s, 1H, H10). 13C-NMR (151 MHz, CDCl 3) δ 163.1 (C9), 147.9 (C1), 142.6 (C11), 136.4 (C7), 129.5 (C3), 129.5 (C13), 129.4 (C2), 128.4 (C12), 127.5 (C5), 126.8 (C6), 126.6 (C14), 126.3 (C4),
122.0 (C8), 60.1 (C10). HRMS for [C22H18N]+ calculated 296.1434 found 296.1421. Rf
Experimental 143
5.2.2.3 Allylation of heterocycles in flow
GP(IV): A 5 mL conical shape microwave vial was charged with the cyanoarene
(1.0 mmol, 1.0 equiv.), the allyl boronic pinacol ester (2.5 mmol, 2.5 equiv), and the photoredox catalyst [Ir(dF(CF3)ppy)2(dtbpy)]PF6 (Ir-3, 6.0 mg, 0.5 mol%). Then 1.5 mL
of acetone was added to obtain a clear yellow transparent 0.5 M solution (2.0 mL overall volume) after sonication for 1 min. The clear yellow solution was then pumped at 200 µL/min through a Vapourtec UV-150 photochemical reactor (10 mL reactor coil, FEP tubing, τ = 50 min) held at 60°C. Once the reaction mixture has fully be taken up by the pump, the input was swapped to acetone solvent to push the rest of the reaction mixture through the reactor. When the reaction plug was exiting the output stream (yellow to orange colour), the totality of the plug was collected in a vial wrapped in aluminium foil and concentrated in vacuo. The residue was then purified by Bioatage flash column chromatography on KP-NH modified silica gel cartridge (0% to 20% EtOAc in hexane gradient) to yield the pure product.
4-allylpyridine (165)
165 was obtained following GP(IV) as a colourless oil (83 mg, 0.70 mmol) in 70% yield.
1H-NMR (600 MHz, CDCl
3) δ 8.50 (d, J = 6.0 Hz, 2H, H1), 7.11 (d, J = 5.8 Hz, 2H, H2),
5.92 (ddt, J = 16.9, 10.1, 6.7 Hz, 1H, H5), 5.18 – 5.08 (m, 2H, H6), 3.37 (d, J = 6.7 Hz,
2H, H4). 13C-NMR (151 MHz, CDCl3) δ 149.8 (C1), 148.9 (C3), 135.1 (C5), 123.9 (C2),
117.4 (C6), 39.3 (C4). HRMS for [C8H10N]+ calculated 120.0808 found 120.0807. Rf (2:1
Experimental 144
1-allylisoquinoline (201)
201 was obtained following GP(IV) as a colourless oil (119 mg, 0.70 mmol) in 70%
yield. 1H-NMR (600 MHz, CDCl3) δ 8.46 (d, J = 5.7 Hz, 1H, H 2), 8.16 (d, J = 8.5 Hz, 1H, H8), 7.81 (d, J = 8.2 Hz, 1H, H5), 7.67 (t, J = 7.5 Hz, 1H, H6), 7.59 (t, J = 7.7 Hz, 1H, H7), 7.53 (d, J = 5.7 Hz, 1H, H3), 6.22 (ddt, J = 16.8, 10.1, 6.5 Hz, 1H, H11), 5.23 – 5.12 (m, 2H, H12), 4.10 (d, J = 6.5 Hz, 2H, H10). 13C-NMR (151 MHz, CDCl3) δ 159.7 (C1), 142.1 (C2), 136.3 (C4), 135.4 (C11), 129.9 (C6), 127.3 (C8), 127.1 (C9), 127.0 (C7), 125.4 (C5), 119.6 (C3), 116.8 (C12), 40.2 (C10). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3055, 1639, 1623, 1588, 1562, 1500, 1385, 1352, 1340, 1144, 991, 906, 820, 745. HRMS for [C12H12N]+
calculated 170.0964 found 170.0959. Rf (EtOAc/hexane, 2:1) = 0.49.
4-allyl-1H-pyrrolo[2,3-b]pyridine (202)
202 was obtained following GP(IV) (using 5 mL of acetone instead of 1.5 mL because of
the low starting material solubility) as a white solid (113 mg, 0.71 mmol) in 71% yield.
1H-NMR (600 MHz, CDCl 3) δ 11.88 (s, 1H, H1), 8.30 (d, J = 4.9 Hz, 1H, H6), 7.40 (d, J = 3.2 Hz, 1H, H2), 6.96 (d, J = 4.9 Hz, 1H, H5), 6.57 (d, J = 3.3 Hz, 1H, H3), 6.09 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H, H10), 5.19 (dd, J = 25.9, 13.5 Hz, 2H, H11), 3.71 (d, J = 6.7 Hz, 2H, H9). 13C-NMR (151 MHz, CDCl3) δ 148.8 (C7), 142.5 (C6), 141.9 (C4), 135.5 (C10), 124.7 (C2), 120.2 (C8), 116.8 (C5), 115.5 (C11), 98.9 (C3), 37.4 (C9). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 3079, 2917, 2829, 1637, 1588, 1493, 1433, 1403, 1340, 1302, 1276, 989, 902, 809, 719. HRMS for [C10H11N2]+ calculated 159.0917 found 159.0915. Rf (1:1
Experimental 145
5.2.2.4 Arylation of boronic esters with aryl bromides in flow
GP(V): A 10 mL microwave vial was charged with the aryl bromide (0.50 mmol,
1.0 equiv.), the photoredox catalyst Ir(dF(CF3)ppy)2(dtbpy)]PF6 (Ir-3, 6.0 mg, 1.0 mol%),
4,4’-di-tert-butyl-2,2’-bipyridine (6.1 mg, 3 mol%), DMAP (120 mg, 2.0 equiv.) and the benzyl pinacol boronic ester (0.60 mmol, 1.2 equiv). The vial was then transferred in a glovebox where the Ni(COD)2 (6.0 mg, 3 mol%) was added and sealed with a rubber
septum. Then 5.0 mL of acetone was added to obtain a clear yellow to brownish transparent solution after sonication for 1 to 5 min. The clear solution was then pumped at 200 µL/min through a Vapourtec UV-150 photochemical reactor (10 mL reactor coil, FEP tubing, τ = 50 min) held at 35°C. Once the reaction mixture has fully be taken up by the pump, the input was swapped to acetone solvent to push the rest of the reaction mixture through the reactor. When the reaction plug was exiting the output stream (orange colour), the totality of the plug was collected in a vial wrapped in aluminium foil, filtered through a pad of celite® and concentrated in vacuo. The residue was then
immobilised on ISOLUTE® HM-N for easy dry loading and purified by Biotage flash column chromatography on a regular silica gel cartridge (0% to 5% EtOAc in hexane gradient) to yield the pure product.
4-(4-methoxybenzyl)benzonitrile (173)
173 was obtained following GP(V) as a colourless oil (91 mg, 0.61 mmol) in 82% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.57 (d, J = 8.2 Hz, 2H, H3), 7.28 (d, J = 8.3 Hz, 2H, H4),
7.08 (d, J = 8.5 Hz, 2H, H8), 6.86 (d, J = 8.6 Hz, 2H, H9), 3.98 (s, 2H, H6), 3.80 (s, 3H,
H11). 13C-NMR (151 MHz, CDCl3) δ 158.4 (C10), 147.2 (C7), 132.3 (C5), 131.4 (C3),
129.9 (C4), 129.5 (C8), 119.0 (C1), 114.2 (C9), 109.9 (C2), 55.3 (C4), 41.1 (C6). HRMS
for [C15H14NO]+ calculated 224.1075 found 224.1077. Rf (1:4 EtOAc/hexane) = 0.29.
Experimental 146
4-(3,5-dimethoxybenzyl)benzonitrile (247)
247 was obtained following GP(V) as a colourless oil (95 mg, 0.37 mmol) in 75% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.58 (d, J = 8.3 Hz, 2H, H3), 7.30 (d, J = 8.3 Hz, 2H, H4),
6.35 (t, J = 2.2 Hz, 1H, H10), 6.31 (d, J = 2.2 Hz, 2H, H8), 3.96 (s, 2H, H6), 3.77 (s, 6H,
H11). 13C-NMR (151 MHz, CDCl3) δ 161.1 (C9), 146.4 (C5), 141.5 (C7), 132.3 (C3),
129.6 (C4), 119.0 (C1), 110.1 (C2), 107.2 (C8), 98.3 (C10), 55.3 (C11), 42.1 (C6). HRMS
for [C16H16NO2]+ calculated 254.1181 found 254.1192. Rf (1:4 EtOAc/hexane) = 0.23.
Spectroscopic data were consistent with literature values.[271]
methyl 4-(4-cyanobenzyl)benzoate (248)
248 was obtained following GP(V) as a colourless oil (90 mg, 0.36 mmol) in 71% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.99 (d, J = 8.3 Hz, 2H, H9), 7.59 (d, J = 8.2 Hz, 2H, H3),
7.28 (d, J = 8.3 Hz, 2H, H4), 7.24 (d, J = 8.2 Hz, 2H, H8), 4.09 (s, 2H, H6), 3.91 (s, 3H,
H12).13C-NMR (151 MHz, CDCl3) δ 166.8 (C11), 145.6 (C7), 144.5 (C5), 132.4 (C3),
130.1 (C9), 129.7 (C4), 129.0 (C10), 128.7 (C8), 118.8 (C1), 110.4 (C2), 52.1 (C12), 41.9
(C6). HRMS for [C16H14NO2]+.calculated 252.1025 found 252.1029. Rf (1:4
Experimental 147
4-(3,5-bis(trifluoromethyl)benzyl)benzonitrile (249)
249 was obtained following GP(V) as a colourless oil (100 mg, 0.30 mmol) in 61% yield.
1H-NMR (600 MHz, CDCl 3) δ 7.78 (s, 1H, H1), 7.65 (d, J = 8.2 Hz, 2H, H9), 7.62 (s, 2H, H4), 7.30 (d, J = 8.2 Hz, 2H, H8), 4.18 (s, 2H, H6).13C-NMR (151 MHz, CDCl3) δ 144.1 (C7), 141.7 (C5), 132.6 (C9), 132.1 (q, J = 33.4 Hz, C3), 129.6 (C4), 129.0 (C2), 124.0 (C8), 120.9 (C1), 118.5 (C11), 111.1 (C10), 41.4 (C6). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2929, 2222, 1624, 1607, 1508, 1467, 1433, 1376, 1274, 1161, 1116, 898. HRMS for [C16H10NF6]+
calculated 330.0717 found 330.0730. Rf (1:4 EtOAc/hexane) = 0.17.
4-(4-methylbenzyl)benzonitrile (250)
250 was obtained following GP(V) as colourless needles (80 mg, 0.38 mmol) in 77%
yield. 1H-NMR (600 MHz, CDCl
3) δ 7.57 (d, J = 8.3 Hz, 2H, H3), 7.29 (d, J = 8.3 Hz,
2H, H4), 7.13 (d, J = 7.9 Hz, 2H, H8), 7.06 (d, J = 7.9 Hz, 2H, H9), 4.00 (s, 2H, H6), 2.34
(s, 3H, H11). 13C-NMR (151 MHz, CDCl3) δ 147.1 (C5), 136.3 (C7 and C10), 132.2 (C4
and C3), 129.5 (C9), 128.8 (C8), 119.0 (C1), 109.9 (C2), 41.6 (C6), 21.0 (C11). HRMS for
[C15H14N]+ calculated 208.1126 found 208.1133. Rf (1:4 EtOAc/hexane) = 0.45. M.p.
Experimental 148
4-(4-fluorobenzyl)benzonitrile (251)
251 was obtained following GP(V) as a colourless oil (56 mg, 0.26 mmol) in 53% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.59 (d, J = 8.3 Hz, 2H, H3), 7.27 (d, J = 8.3 Hz, 2H, H4),
7.12 (dd, J = 8.6, 5.4 Hz, 2H, H8), 7.01 (t, J = 8.7 Hz, 2H, H9), 4.01 (s, 3H). 13C-NMR
(151 MHz, CDCl3) δ 161.7 (d, J = 245 Hz, C10), 146.5 (C5), 135.0 (d, J = 3.3 Hz, C7),
132.4 (C3), 130.4 (d, J = 7.9 Hz, C8), 129.5 (C4), 118.9 (C1), 115.6, (d, J = 21 Hz, C9),
110.2 (C2), 41.1 (C6). HRMS for [C14H11NF]+ calculated 212.0876 found 212.0883. Rf (1:4 EtOAc/hexane) = 0.42. Spectroscopic data were consistent with literature
values.[281]
1-methoxy-4-(4-(trifluoromethyl)benzyl)benzene (172)
172 was obtained following GP(V) as a colourless oil (95 mg, 0.36 mmol) in 71% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.55 (d, J = 8.1 Hz, 2H, H3), 7.30 (d, J = 8.0 Hz, 2H, H4),
7.11 (d, J = 8.7 Hz, 2H, H8), 6.87 (d, J = 8.7 Hz, 2H, H9), 3.99 (s, 2H, H6), 3.81 (s, 3H,
H11). 13C-NMR (151 MHz, CDCl3) δ 158.2 (C10), 145.7 (C5), 132.1 (C7), 129.9 (C8),
129.0 (C4), 128.4 (q, J = 32 Hz, C2), 125.3 (q, J = 3.7 Hz, C3), 124.2 (q, J = 272 Hz, C1),
114.1 (C9), 55.6 (C11), 40.8 (C6). HRMS for [C15H14OF3]+ calculated 267.0997 found
267.0989. Rf (1:4 EtOAc/hexane) = 0.46. Spectroscopic data were consistent with
Experimental 149
4-(4-methoxybenzyl)benzaldehyde (252)
252 was obtained following GP(V) as a colourless oil (96 mg, 0.42 mmol) in 85% yield.
1H-NMR (600 MHz, CDCl
3) δ 9.98 (s, 1H, H12), 7.81 (d, J = 8.0 Hz, 2H, H3), 7.35 (d, J
= 8.0 Hz, 2H, H4), 7.11 (d, J = 8.7 Hz, 2H, H8), 6.86 (d, J = 8.7 Hz, 2H, H9), 4.01 (s, 2H,
H6), 3.80 (s, 3H, H11). 13C-NMR (151 MHz, CDCl3) δ 192.0 (C1), 158.3 (C10), 149.0
(C5), 134.6 (C5), 131.8 (C7), 130.0 (C8), 129.9 (C3), 129.4 (C4), 114.1 (C9), 55.3 (C11),
41.2 (C6). HRMS for [C15H15O2]+ calculated 227.1072 found 227.1071. Rf (1:4
EtOAc/hexane) = 0.26. Spectroscopic data were consistent with literature values.[283]
1-(4-methoxybenzyl)-2-methylbenzene (253)
253 was obtained following GP(V) as a colourless oil (53 mg, 0.25 mmol) in 50% yield.
1H-NMR (600 MHz, CDCl
3) δ 7.20 – 7.13 (m, 3H, H9, H10 and H11), 7.11 – 7.08 (m, 1H,
H12), 7.05 (d, J = 8.7 Hz, 2H, H4), 6.83 (d, J = 8.7 Hz, 2H, H3), 3.94 (s, 2H, H6), 3.79 (s,
3H, H1), 2.26 (s, 3H, H13). 13C-NMR (151 MHz, CDCl3) δ 157.8 (C2), 139.3 (C7), 136.5
(C8), 132.4 (C5), 130.2 (C9), 129.8 (C12), 129.7 (C4), 126.3 (C10), 125.9 (C11), 113.8 (C3),
55.2 (C1), 38.5 (C6), 19.6 (C13). HRMS for [C15H16O]+ calculated 212.1201 found
212.1202. Rf (1:4 EtOAc/hexane) = 0.54. Spectroscopic data were consistent with
Experimental 150
1-methoxy-4-(4-vinylbenzyl)benzene (254)
254 was obtained following GP(V) as a colourless oil (81 mg, 0.36 mmol) in 72% yield. 1H-NMR (600 MHz, CDCl3) δ 7.36 (d, J = 8.1 Hz, 2H, H 3), 7.16 (d, J = 8.1 Hz, 2H, H4), 7.13 (d, J = 8.7 Hz, 2H, H8), 6.86 (d, J = 8.7 Hz, 2H, H9), 6.71 (dd, J = 17.6, 10.9 Hz, 1H, H1), 5.73 (dd, J = 17.6, 0.7 Hz, 1H, H12cis), 5.22 (dd, J = 10.9, 0.7 Hz, 1H, H12trans), 3.94 (s, 2H, H6), 3.80 (s, 3H, H11).13C-NMR (151 MHz, CDCl3) δ 157.9 (C10), 141.3 (C5), 136.6 (C1), 135.4 (C2), 133.1 (C7), 129.9 (C8), 129.0 (C4), 126.3 (C3), 113.9 (C9), 113.2
(C12), 55.3 (C11), 40.8 (C6). HRMS for [C16H17O]+ calculated 225.1279 found 225.1274. Rf (1:4 EtOAc/hexane) = 0.51. Spectroscopic data were consistent with literature
values.[284]
((4-(4-methoxybenzyl)phenyl)ethynyl)trimethylsilane (255)
255 was obtained following GP(V) as a colourless oil (91 mg, 75% yield). 1H-NMR (600 MHz, CDCl3) δ 7.39 (d, J = 8.2 Hz, 2H, H9), 7.11 (d, J = 8.2 Hz, 2H, H8), 7.07 (d, J = 8.7
Hz, 2H, H4), 6.84 (d, J = 8.7 Hz, 2H, H3), 3.92 (s, 2H, H6), 3.79 (s, 3H, H1), 0.25 (s, 9H,
H13). 13C-NMR (151 MHz, CDCl3) δ 158.1 (C2), 142.2 (C7), 132.6 (C5), 132.1 (C9),
129.8 (C4), 128.7 (C8), 120.7 (C10), 113.9 (C3), 105.2 (C11), 93.6 (C12), 55.2 (C1), 40.9
(C6), 0.0 (C13). IR (ATR – neat) 𝑣̃ (𝑐𝑚−1) = 2956, 2901, 2155, 1609, 1584, 1510, 1504,
1455, 1441, 1300, 1243, 1175, 1031, 840, 813, 755. HRMS for [C19H22OSi]+ calculated
Experimental 151
4-(4-methoxybenzyl)phenol (257)
257 was obtained following GP(V) using 2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-
dioxaborolane as arylbromide followed by an NaOH/H2O2 oxidation of the aryl pinacol
ester product as described by Molander.[229] The corresponding phenol (257) was then isolated as a white amorphous solid (76 mg, 0.36 mmol) in 71% yield. 1H-NMR (600 MHz, CDCl3) δ 7.12 (d, J = 8.7 Hz, 2H, H8), 7.06 (d, J = 8.5 Hz, 2H, H4), 6.86 (d, J = 8.7
Hz, 2H, H9), 6.77 (d, J = 8.5 Hz, 2H, H3), 5.31 (br s, 1H, H1), 3.88 (s, 2H, H6), 3.81 (s,
3H, H11).13C-NMR (151 MHz, CDCl3) δ 157.8 (C10), 153.7 (C2), 133.8 (C7 and C5),
130.0 (C4), 129.8 (C8), 115.3 (C3), 113.9 (C9), 55.3 (C11), 40.1 (C6). HRMS for
[C14H14O2]+ calculated 214.0994 found 214.0986. Rf (1:4 EtOAc/hexane) = 0.13.
Experimental 152