ꢀ
E. Lopusanskaja, A. Kooli, A. Paju et al.
Tetrahedron 83 (2021) 131935
2.23 (s, 3H); 13C NMR (101 MHz, CDCl3):
d
¼ 150.0, 140.0, 130.0,
131.3, 129.0, 128.7, 128.1, 127.9, 124.1, 74.0, 16.5; HRMS (ESI): m/z
[MþH]þ calculated for C15H16O 213.1274, found 213.1262.
129.9, 128.8, 128.7, 127.1, 126.5, 36.8, 20.7; HRMS (ESI): m/z [M ꢁ H]-
calculated for C21H20O 287.1441, found 287.1459.
4.4.18. 6-Benzyl-2,6-dimethylcyclohexa-2,4-dien-1-one (3f)
4.4.12. 1-(Benzyloxy)-2-(tert-butyl)-benzene (2d)
Following GPB 3f (119 mg, 56%) as a green viscous oil was ob-
tained after purification; IR (neat) nmax: 3029, 2974, 2922, 1715,
1677, 1655, 1639, 1582, 1495, 1452, 1376, 1072, 1019, 738, 702,
Following GPA 2d (39 mg, 16%) as a colourless oil was obtained
after purification; IR (neat) nmax: 2961, 1744, 1608, 1513, 1455, 1364,
1295, 1244, 1182, 1025, 828, 735, 697, 553 cmꢁ1; 1H NMR (400 MHz,
512 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
7.17 (d, J ¼ 7.2 Hz, 3H), 7.02
CDCl3)
2H), 7.21 (ddd, J ¼ 8.2, 7.3, 1.7 Hz, 1H), 7.00e6.92 (m, 2H), 5.16 (s,
2H), 1.46 (s, 9H); 13C NMR (101 MHz, CDCl3)
157.7, 138.5, 137.6,
d
7.51 (d, J ¼ 7.3 Hz, 2H), 7.46e7.40 (m, 2H), 7.40e7.33 (m,
(dd, J ¼ 7.5, 2.0 Hz, 2H), 6.63 (dt, J ¼ 6.0, 1.6 Hz, 1H), 6.22 (ddd,
J ¼ 9.5, 1.8, 0.9 Hz, 1H), 6.05 (dd, J ¼ 9.5, 6.0 Hz, 1H), 3.17 (d,
d
J ¼ 13.0 Hz,1H), 2.74 (d, J ¼ 13.0 Hz,1H),1.79 (s, 3H), 1.25 (s, 3H); 13
C
128.7, 127.8, 127.4, 127.2, 126.9, 120.7, 112.6, 70.2, 35.0, 30.0; HRMS
NMR (101 MHz, CDCl3) d 205.6, 144.6, 138.2, 137.2, 133.3, 129.8,
(ESI): m/z [MþH]þ calculated for C17H20O 241.1587, found 241.1576.
127.8, 126.5, 120.6, 52.0, 46.7, 24.9, 15.5; HRMS (ESI): m/z [MþNa]þ
calculated for C15H16O 235.1093, found 235.1086.
4.4.13. 2-Benzyl-6-(tert-butyl)-phenol (3d)
Following GPA 3d (15 mg, 6%) after purification as a green oil
was obtained; IR (neat) nmax: 3560, 3062, 3028, 2958, 1603, 1494,
1437, 1391, 1361, 1247, 1206, 1134, 1088, 1029, 887, 844, 797, 776,
4.4.19. 4-Benzyl-2,6-dimethylphenol (4f)
Following GPA 4f (136 mg, 64%) as a yellow solid was obtained
after purification; mp 62e64 ꢀC; IR (KBr) nmax: 3395, 3026, 2915,
1603, 1490, 1452, 1385, 1348, 1303, 1212, 1147, 1030, 960, 879, 780,
747, 699, 532, 458 cmꢁ1 1H NMR (400 MHz, CDCl3)
; d 7.33 (t,
J ¼ 7.2 Hz, 2H), 7.29e7.25 (m, 1H), 7.23 (d, J ¼ 7.7 Hz, 3H), 7.03 (dd,
726, 695, 657, 589, 494, 449 cmꢁ1 1H NMR (400 MHz, CDCl3)
;
J ¼ 7.4, 1.6 Hz, 1H), 6.87 (t, J ¼ 7.6 Hz, 1H), 4.77 (s, 1H), 4.01 (s, 2H),
d
7.45e7.25 (m, 2H), 7.21 (ddt, J ¼ 7.4, 3.0, 1.8 Hz, 3H), 6.83 (s, 2H),
1.40 (s, 9H); 13C NMR (101 MHz, CDCl3)
d 153.1, 139.0, 136.8, 129.1,
4.52 (s, 1H), 3.87 (s, 2H), 2.22 (s, 6H); 13C NMR (101 MHz, CDCl3)
129.0, 128.7, 127.0, 126.8, 125.8, 120.3, 37.3, 34.7, 30.0; HRMS (ESI):
d 150.6, 141.9, 132.9, 129.2, 128.9, 128.5, 126.0, 123.1, 41.2, 16.0;
m/z [M ꢁ H]- calculated for C17H20O 239.1441, found 239.1448.
HRMS (ESI): m/z [M ꢁ H]- calculated for C15H16O 211.1128, found
211.1124.
4.4.14. 4-Benzyl-2-(tert-butyl)-phenol (4d)
Following GPA 4d (46 mg, 19%) as a brown oil was obtained after
4.4.20. 2-(Benzyloxy)-1,3,5-trimethylbenzene (2h)
purification; IR (neat) nmax: cmꢁ1
d
;
1H NMR (400 MHz, CDCl3)
Following GPB 2h (22 mg (10%) as a colorless oil was obtained
after purification; IR (neat) nmax: 2920, 1483, 1454, 1373, 1307, 1213,
7.35e7.27 (m, 2H), 7.24e7.18 (m, 3H), 7.13 (d, J ¼ 2.2 Hz, 1H), 6.86
(dd, J ¼ 8.0, 2.2 Hz, 1H), 6.59 (d, J ¼ 8.0 Hz, 1H), 4.71 (s, 1H), 3.93 (s,
2H), 1.41 (s, 9H); 13C NMR (101 MHz, CDCl3)
152.6, 141.8, 136.1,
1147, 1020, 857, 727, 696, 573 cmꢁ1 1H NMR (400 MHz, CDCl3)
;
d
d
7.57e7.51 (m, 2H), 7.48e7.42 (m, 2H), 7.42e7.36 (m, 1H), 6.90 (s,
133.1, 129.0, 128.5, 127.9, 127.3, 126.0, 116.7, 41.5, 34.6, 29.7; HRMS
(ESI): m/z [M ꢁ H]- calculated for C17H20O 239.1441, found
239.1443.
2H), 4.84 (s, 2H), 2.33 (s, 6H), 2.31 (s, 3H); 13C NMR (101 MHz,
CDCl3)
d 153.7, 137.9, 133.4, 130.8, 129.6, 128.6, 128.0, 127.9, 74.2,
20.8, 16.4; HRMS (ESI): m/z [MþNa]þ calculated for C16H18
O
249.1250, found 249.1253.
4.4.15. 1-(Benzyloxy)-4-(tert-butyl)-benzene (2e)
Following GPA 2e (139 mg, 58%) as a white solid was obtained
after purification; mp 61e63 ꢀC; IR (KBr) nmax: 2952, 2931, 2866,
1608, 1514, 1454, 1363, 1299, 1243, 1187, 1125, 914, 837, 811, 750,
4.4.21. 6-Benzyl-2,4,6-trimethylcyclohexa-2,4-dien-1-one (3h)
Following GPB 3h (190 mg, 84%) as a white solid was obtained
after purification; mp 43e45 ꢀC; IR (KBr) nmax: 3449, 3060, 3027,
2977, 2918, 2862, 1667, 1638, 1585, 1495, 1449, 1383, 1237, 1190,
1074,1018, 983, 949, 855, 772, 746, 703, 603, 565, 503, 424 cmꢁ1; 1H
701, 555, 514 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
7.48e7.43 (m, 2H),
7.43e7.37 (m, 2H), 7.36e7.29 (m, 3H), 6.99e6.89 (m, 2H), 5.06 (s,
2H), 1.32 (s, 9H); 13C NMR (101 MHz, CDCl3)
156.7, 143.7, 137.4,
d
NMR (400 MHz, CDCl3)
d
7.23e7.09 (m, 3H), 7.00 (dd, J ¼ 7.5, 2.1 Hz,
128.7, 128.0, 127.6, 126.4, 114.4, 70.2, 34.2, 31.7; HRMS (ESI): m/z
2H), 6.46 (dq, J ¼ 2.8, 1.5 Hz, 1H), 5.87 (s, 1H), 3.08 (d, J ¼ 12.8 Hz,
1H), 2.70 (d, J ¼ 12.9 Hz, 1H), 1.82 (d, J ¼ 1.6 Hz, 3H), 1.76 (s, 3H), 1.21
[MþNa]þ calculated for C17H20O 263.1406, found 263.1393.
(s, 3H); 13C NMR (101 MHz, CDCl3)
d 205.7, 142.5, 138.9, 137.4, 132.8,
129.9, 128.0, 127.6, 126.4, 51.1, 47.2, 25.0, 21.2, 15.4; HRMS (ESI): m/z
4.4.16. 2-Benzyl-4-(tert-butyl)-phenol (3e)
[MþNa]þ calculated for C16H18O 249.1250, found 249.1250.
Following GPA 3e (10 mg, 4%) after purification as a white solid
was obtained; mp 48e50 ꢀC; IR (KBr) nmax: 3346, 2962, 1637, 1551,
1509, 1469, 1429, 1385, 1365, 1318, 1270, 1220, 1175, 1124, 1093,
1031, 953, 816, 770, 730, 698, 605 cmꢁ1; 1H NMR (400 MHz, CDCl3)
4.4.22. 4-Benzyl-2,4,6-trimethylcyclohexa-2,5-dien-1-one (4h)
Following GPA 4h (73 mg, 32%) as a colourless oil was obtained
after purification; IR (neat) nmax: 3028, 2963, 2923, 1669, 1635,
1495, 1452, 1400, 1374, 1217, 1039, 1015, 916, 776, 740, 702,
d
7.43e7.36 (m, 2H), 7.36e7.28 (m, 3H), 7.28e7.21 (m, 2H),
6.86e6.77 (m, 1H), 4.63 (s, 1H), 4.10 (s, 2H), 1.39 (d, J ¼ 0.5 Hz, 9H);
13C NMR (101 MHz, CDCl3)
d
151.6, 143.8, 140.2, 128.8, 128.7, 128.2,
478 cmꢁ1
;
1H NMR (400 MHz, CDCl3)
d
7.27e7.16 (m, 3H),
126.4, 126.2, 124.7, 115.4, 37.0, 34.2, 31.7; HRMS (ESI): m/z [MþNa]þ
7.09e6.96 (m, 2H), 6.59 (s, 2H), 2.79 (s, 2H), 1.83 (s, 6H), 1.22 (s, 3H);
calculated for C17H20O 263.1406, found 263.1402.
13C NMR (101 MHz, CDCl3)
d 187.3, 150.5, 136.7, 134.2, 130.2, 127.9,
126.8, 47.3, 41.7, 25.3, 16.2; HRMS (ESI): m/z [MþNa]þ calculated for
C16H18O 249.1250, found 249.1251.
4.4.17. 2-(Benzyloxy)-1,3-dimethylbenzene (2f)
Following GPA 2f (23 mg, 11%) after purification as a colorless oil
was obtained; IR (neat) nmax: 3031, 2922. 2860, 1591, 1496, 1476,
1454, 1373, 1263, 1198, 1091, 1013, 915, 859, 769, 734, 698, 562,
4.4.23. 2-(Benzyloxy)-1,3-dimethoxy-5-methylbenzene (2i)
Following GPA 2i (85 mg, 33%) as a yellow oil was obtained after
purification; IR (neat) nmax: 2938, 1591, 1505, 1464, 1415, 1374, 1332,
462 cmꢁ1
;
1H NMR (400 MHz, CDCl3)
d
7.56e7.49 (m, 2H),
7.48e7.36 (m, 3H), 7.11e7.04 (m, 2H), 6.99 (dd, J ¼ 8.2, 6.6 Hz, 1H),
4.85 (s, 2H), 2.35 (s, 6H); 13C NMR (101 MHz, CDCl3)
155.9, 137.9,
1238, 1129, 1011, 969, 914, 814, 734, 698, 585, 528 cmꢁ1 1H NMR
;
d
(400 MHz, CDCl3) d 7.60e7.44 (m, 2H), 7.42e7.27 (m, 3H), 6.39 (s,
7