Molecules 2021, 26, 3366
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134.8 (q), 133.7 (q), 131.4 (q), 129.9 (CH), 129.3 (CH), 128.3 (CH), 126.5 (CH), 123.9 (CH),
122.7 (q), 113.9 (CH), 62.1 (CH2), 55.4 (CH3), 43.1 (CH2), 21.1 (CH3), 14.7 (CH3); MS (EI
ion source): m/z (%) = 323 (43, [M+]), 294 (87), 250 (100), 235 (20), 207 (17); HRMS: m/z
[M + H]+ calcd. for C20H22NO3: 324.1594; found: 324.1597.
Compound 2g. Yield: 96% (112.4 mg); orange wax; IR (neat): 2980, 2243, 1705, 1596,
1494 cm−1; 1H NMR (400.13 MHz) (CDCl3):
δ = 7.99 (d, J = 8.4 Hz, 2H), 7.54–7.52 (m, 1H),
7.45 (d, J = 8.4 Hz, 2H), 7.11–7.07 (m, 1H), 6.79 (bd, J = 1.4 Hz, 1H), 6.08 (t, J = 4.4 Hz, 1H),
4.46 (d, J = 4.4 Hz, 2H), 4.27 (q, J = 7.1 Hz, 2H), 2.64 (s, 3H), 2.23 (s, 3H), 1.34 (t, J = 7.1 Hz,
3H); 13C NMR (100.6 MHz) (CDCl3):
δ = 197.9 (q), 154.2 (q), 144.0 (q), 138.3 (q), 136.5 (q),
134.8 (q), 133.9 (q), 129.6 (CH), 129.0 (CH), 128.7 (CH), 128.6 (CH), 128.5 (q), 126.3 (CH),
124.1 (CH), 62.3 (CH2), 43.1 (CH2), 26.8 (CH3), 21.1 (CH3), 14.7 (CH3); MS (EI ion source):
m/z (%) = 351 (M+, 31), 322 (50), 278 (14), 157 (46), 134 (100), 114 (62); HRMS: m/z [M + H]+
calcd. for C21H22NO3: 336.1594; found: 336.1598.
Compound 2h. Yield: 99% (106.3 mg); yellow oil; IR (neat): 2979, 1703, 1608, 1557,
1376, 1271 cm−1; 1H NMR (400.13 MHz) (CDCl3):
δ
= 7.28–7.14 (m, 6H), 6.68 (s, 1H), 6.01
(t, J = 5.2 Hz, 1H), 4.20–4.14 (m, 4H), 2.26 (s, 3H), 1.65 (s, 3H), 1.24 (t, J = 7.1 Hz, 3H);
13C NMR (100.6 MHz) (CDCl3):
= 153.9 (q), 141.8 (q), 139.9 (q), 139.1 (q), 137.3 (q), 135.3
δ
(q), 129.0 (CH), 128.5 (CH), 127.4 (CH), 127.2 (CH), 125.8 (q), 125.3 (CH), 122.4 (CH), 62.1
(CH2), 42.6 (CH2), 23.0 (CH3), 21.5 (CH3), 14.7 (CH3); MS (EI ion source): m/z (%) = 307 (20,
[M+]), 278 (27), 234 (100), 218 (18); HRMS: m/z [M + H]+ calcd. for C20H22NO2: 308.1645;
found: 308.1649.
Compound 2i. Yield: 56% (61.7 mg); pale yellow oil; IR (neat): 2981, 2847, 1702, 1594,
1
1481 cm−1; H NMR (400.13 MHz) (CDCl3):
δ = 7.59 (bd, J = 8.1 Hz, 1H), 7.43–7.36 (m,
3H), 7.33–7.30 (m, 2H), 7.21 (dd, J1 = 8.7 Hz, J2 = 2.5 Hz, 1H), 7.02 (d, J = 2.5 Hz, 1H), 6.06
(t, J = 4.5 Hz, 1H), 4.47 (d, J = 4.5 Hz, 2H), 4.28 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H);
13C NMR (100.6 MHz) (CDCl3):
δ = 153.9 (q), 138.1 (q), 135.6 (q), 130.7 (q), 129.5 (CH), 128.61
(CH), 128.60 (CH), 128.0 (CH), 127.4 (CH), 125.7 (CH), 125.3 (CH), 124.4 (q), 62.3 (CH2),
43.0 (CH2), 14.5 (CH3). MS (EI ion source): m/z (%) = 313 (30, [M+]), 284 (72), 240 (100), 204
(62), 176 (19); HRMS: m/z [M + H]+ calcd. for C18H17ClNO2: 314.0942; found: 314.0952.
Compound 2j. Yield: 10% (13.0 mg); colorless oil; IR (eat): 2919, 2848, 1710, 1609,
1382, 1051 cm−1; 1H NMR (400.13 MHz) (CDCl3):
δ = 7.77 (bd, J = 8.5 Hz, 1H), 7.49 (dd,
J1 = 8.6 Hz, J2 = 1.6 Hz, 1H), 7.33 (bd, J = 1.6 Hz, 1H), 7.25 (d, J = 8.8 Hz, 2H), 6.94 (d,
J = 8.8 Hz, 2H), 6.04 (t, J = 4.5 Hz, 1H), 4.48 (d, J = 4.5 Hz, 2H), 4.30 (q, J = 7.1 Hz, 2H),
3.86 (s, 3H), 1.36 (t, J = 7.1 Hz, 3H); 13C NMR (100.6 MHz) (CDCl3):
δ = 159.7 (q), 153.9 (q),
140.4 (q), 137.8 (q), 130.4 (q), 129.9 (q), 129.7 (CH), 126.1 (q, q, J = 32.5 Hz), 124.5 (CH, q,
J = 3.7 Hz), 124.20 (q, q, J = 270.3 Hz), 124.19 (CH), 123.7 (CH), 123.1 (CH, q, J = 3.7 Hz),
114.2 (CH), 62.7 (CH2), 55.5 (CH3), 43.2 (CH2), 14.6 (CH3); 19F NMR (376.5 MHz) (CDCl3):
δ
=
−
62.3; MS (EI ion source): m/z (%) = 377 (26, [M+]), 348 (77), 304 (100), 289 (14), 261
(18); HRMS: m/z [M + Na]+ calcd. for C20H18F3NO3Na: 400.1131; found: 400.1119.
Isomeric mixture 2k
20k. Overall yield (catalyst A): 99% (107.2.0 mg); 2k 20k = 67/33;
+
/
overall yield (catalyst A0): 99% (107.1 mg); 2k 20k = 94/6; overall yield (catalyst B): 90%
/
(97.1 mg); 2k/20k = 44/56; overall yield (catalyst C): 67% (72.7 mg); 2k/20k = 46/54.
2k: orange oil; IR (Neat): 2980, 2243, 1705, 1596, 1494 cm−1; 1H NMR (400.13 MHz)
(CDCl3):
1H), 5.80 (t, J = 4.5 Hz, 1H), 4.38 (d, J = 4.6 Hz, 2H), 4.21 (q, J = 7.1 Hz, 2H), 3.74 (s, 3H), 1.27
(t, J = 7.1 Hz, 3H); 13C NMR (100.6 MHz) (CDCl3):
= 159.1 (q), 154.1 (q), 139.2 (q), 138.7
δ = 7.29–7.21 (m, 6H), 6.90 (d, J = 8.7 Hz, 1H), 6.52 (dd, J1 = 8.7 Hz, J2 = 2.6 Hz,
δ
(q), 138.6 (q), 128.8 (CH), 128.5 (CH), 127.8 (CH), 127.0 (CH), 122.5 (q), 120.4 (CH), 110.2
(CH), 109.7 (CH), 62.3 (CH2), 55.5 (CH3), 43.3 (CH2), 14.7 (CH3). MS (EI ion source): m/z
(%) = 309 (0.2, [M+]), 235 (100), 220 (17), 204 (29), 191 (24), 165 (15); HRMS: m/z [M + Na]+
calcd. for C19H19NO3Na: 332.1257; found: 332.1260.
20k: colorless oil; IR (neat): 2982, 1708, 1610, 1504, 1466 cm−1; 1H NMR (400.13 MHz)
(CDCl3):
J = 5.1 Hz, 2H), 4.29 (q, J = 7.2 Hz, 2H), 3.43 (s, 3H), 1.35 (t, J = 7.2 Hz, 3H); 13C NMR
(100.6 MHz) (CDCl3): = 156.2 (q), 153.9 (q), 141.5 (q), 139.8 (q), 137.8 (q), 128.3 (CH), 127.7
δ = 7.36–7.24 (m, 6H), 6.69 (d, J = 8.9 Hz, 1H), 6.08 (t, J = 5.1 Hz, 1H), 4.33 (d,
δ