813, 790, 736, 710; 1H NMR (400 MHz, CDCl3) δ 8.08-8.04 (2H,
m, ArH), 7.65 (1H, d, J = 2.4 Hz, ArH), 7.57 (1H, tt, J = 7.4, 1.4
Hz, ArH), 7.45 (2H, dddd, J = 8.1, 7.4, 1.4, 1.4 Hz, ArH), 7.19
(1H, dd, J = 8.2, 2.4 Hz, ArH), 7.13 (1H, d, J = 8.2 Hz, ArH),
4.38 (2H, t, J = 6.2 Hz, OCH2), 4.03 (1H, s, NCHCO), 2.97-2.83
(2H, m, CH2Ar), 2.25 (6H, s, N(CH3)2), 2.20-2.01 (2H, m,
CH2CH2CH2), 1.38 (9H, s, tBu); 13C NMR (100 MHz, CDCl3) δ
170.4, 166.4, 138.6, 137.2, 132.9, 132.4, 130.9, 130.2, 129.5,
128.6, 128.3, 128.0, 81.6, 70.4, 64.2, 43.1, 30.2, 28.8, 27.8;
HRMS (ESI): calcd for C24H31ClNO4 [M + H]+ 432.1936, found
432.1921.
81.2, 80.4, 72.72, 72.69, 63.3, 62.9, 42.0, 41.9, 41.2, 41.1, 32.7,
31.4, 28.4, 27.9, 21.1, 20.9; HRMS (ESI): calcd for C25H34NO4
[M + H]+ 412.2482, found 412.2472.
3.20. 5-(tert-Butoxy)-4-(dimethylamino)-3-(4-methoxyphenyl)-5-
oxopentyl benzoate (4m)
Isolated as a 5/5 mixture of diastereomers. Yellow oil; IR (ATR)
νmax/cm-1 3005, 2962, 2932, 2869, 2833, 2790, 2770, 1712, 1612,
1584, 1513, 1469, 1450, 1390, 1366, 1313, 1271, 1245, 1175,
1145, 1116, 1069, 1035, 1025, 1006, 942, 911, 829, 817, 791,
734, 710; 1H NMR (400 MHz, CDCl3) δ 8.00-7.92 (2H, m, ArH),
7.58-7.50 (1H, m, ArH), 7.46-7.37 (2H, m, ArH), 7.16-7.08 (2H,
m, ArH), 6.84 (1H, ddd, J = 8.4, 2.4, 2.4 Hz, ArH), 6.80 (1H,
ddd, J = 8.4, 2.4, 2.4 Hz, ArH), 4.21 (0.5H, ddd, J = 11.1, 6.8, 5.0
Hz, 1-H), 4.16 (0.5H, ddd, J = 11.0, 6.6, 4.8 Hz, 1-H), 4.08
(0.5H, ddd, J = 11.1, 8.5, 6.0 Hz, 1-H), 4.00 (0.5H, ddd, J = 11.0,
8.4, 6.2 Hz, 1-H), 3.76 (1.5H, s, OCH3), 3.75 (1.5H, s, OCH3),
3.33 (0.5H, d, J = 11.2 Hz, 4-H), 3.29 (0.5H, d, J = 11.6 Hz, 4-
H), 3.18 (0.5H, ddd, J = 11.2, 11.2, 3.2 Hz, 3-H), 3.12 (0.5H,
ddd, J = 11.6, 11.6, 3.2 Hz, 3-H), 2.57 (0.5H, dddd, J = 14.0, 8.5,
6.8, 3.2 Hz, 2-H), 2.42 (3H, s, N(CH3)2), 2.26 (3H, s, N(CH3)2),
2.07 (0.5H, dddd, J = 14.0, 8.4, 6.6, 3.2 Hz, 2-H), 1.93-1.78 (1H,
m, 2-H), 1.51 (4.5H, s, tBu), 1.15 (4.5H, s, tBu); 13C NMR (100
MHz, CDCl3) δ 170.3, 169.4, 166.4, 166.3, 158.5, 158.2, 132.8,
132.75, 132.71, 132.4, 130.34, 130.29, 129.7, 129.5, 129.4,
128.9, 128.23, 128.22, 113.9, 113.7, 81.3, 80.4, 72.8, 63.3, 62.9,
55.2, 55.0, 41.6, 41.5, 41.2, 41.1, 32.7, 31.4, 28.4, 27.9; HRMS
(ESI): calcd for C25H34NO5 [M + H]+ 428.2431, found 428.2422.
3.17. 3-(4-Bromo-2-(2-(tert-butoxy)-1-(dimethylamino)-2-
oxoethyl)phenyl)propyl benzoate (2k)
Colorless oil; IR (ATR) νmax/cm-1 3062, 2977, 2954, 2868, 2821,
2774, 1716, 1602, 1586, 1479, 1451, 1392, 1367, 1348, 1314,
1270, 1220, 1174, 1141, 1110, 1069, 1042, 1026, 960, 905, 890,
1
837, 809, 735, 710; H NMR (400 MHz, CDCl3) δ 8.05 (2H, dd,
J = 7.9, 1.2 Hz, ArH), 7.79 (1H, d, J = 2.0 Hz, ArH), 7.57 (1H, t,
J = 7.6 Hz, ArH), 7.45 (2H, dd, J = 7.9, 7.6 Hz, ArH), 7.34 (1H,
dd, J = 8.2, 2.0 Hz, ArH), 7.07 (1H, d, J = 8.2 Hz, ArH), 4.37
(2H, t, J = 6.2 Hz, OCH2), 4.01 (1H, s, NCHCO), 2.96-2.80 (2H,
m, CH2Ar), 2.25 (6H, s, N(CH3)2), 2.19-2.01 (2H, m,
CH2CH2CH2), 1.38 (9H, s, tBu); 13C NMR (100 MHz, CDCl3) δ
170.4, 166.5, 139.1, 137.6, 133.0, 131.5, 131.3, 131.0, 130.3,
129.6, 128.4, 120.4, 81.7, 70.5, 64.2, 43.2, 30.2, 28.9, 27.9;
HRMS (ESI): calcd for C24H31BrNO4 [M + H]+ 476.1431, found
476.1410.
3.18. 3-(2-(2-(tert-Butoxy)-1-(dimethylamino)-2-oxoethyl)-4-
methylphenyl)propyl benzoate (2l)
3.21. 3-(2-(2-(tert-Butoxy)-1-(dimethylamino)-2-oxoethyl)-5-
chlorophenyl)propyl benzoate (2n)
Yellow oil; IR (ATR) νmax/cm-1 2925, 2856, 2819, 2771, 1717,
1638, 1602, 1584, 1501, 1451, 1391, 1367, 1314, 1270, 1215,
1142, 1114, 1069, 1042, 1026, 963, 936, 902, 843, 815, 789, 711;
1H NMR (400 MHz, CDCl3) δ 8.07 (2H, dd, J = 8.2, 1.4 Hz,
ArH), 7.57 (1H, tt, J = 7.6, 1.4 Hz, ArH), 7.48-7.41 (3H, m,
ArH), 7.07 (1H, d, J = 7.6 Hz, ArH), 7.02 (1H, dd, J = 7.6, 1.6
Hz, ArH), 4.37 (2H, t, J = 6.4 Hz, OCH2), 4.03 (1H, s, NCHCO),
2.89 (2H, t, J = 7.8 Hz, CH2Ar), 2.30 (3H, s, ArCH3), 2.25 (6H, s,
Colorless oil; IR (ATR) νmax/cm-1 2977, 2954, 2931, 2868, 2820,
2773, 1716, 1597, 1569, 1478, 1451, 1391, 1367, 1314, 1270,
1221, 1140, 1112, 1069, 1043, 1026, 949, 901, 882, 836, 790,
710; 1H NMR (400 MHz, CDCl3) δ 8.07 (2H, dd, J = 8.0, 1.2 Hz,
ArH), 7.60-7.53 (2H, m, ArH), 7.46 (2H, dd, J = 8.0, 7.2 Hz,
ArH), 7.23-7.18 (2H, m, ArH), 4.40 (2H, t, J = 6.2 Hz, OCH2),
4.02 (1H, s, NCHCO), 2.97-2.83 (2H, m, CH2Ar), 2.23 (6H, s,
N(CH3)2), 2.20-2.03 (2H, m, CH2CH2CH2), 1.36 (9H, s, tBu); 13
C
N(CH3)2), 2.19-2.03 (2H, m, CH2CH2CH2), 1.36 (9H, s, tBu); 13
C
NMR (100 MHz, CDCl3) δ 170.7, 166.5, 142.2, 133.9, 133.6,
133.0, 130.3, 130.1, 129.6, 129.5, 128.4, 126.8, 81.5, 70.1, 64.3,
43.1, 30.2, 29.2, 27.9; HRMS (ESI): calcd for C24H31ClNO4 [M +
H]+ 432.1936, found 432.1923.
NMR (100 MHz, CDCl3) δ 169.7, 166.6, 137.0, 136.1, 132.9,
130.4, 129.58, 129.57, 128.9, 128.7, 128.3, 70.5, 64.4, 43.3, 30.4,
29.7, 29.0, 27.9, 21.0; HRMS (ESI): calcd for C25H34NO4 [M +
H]+ 412.2482, found 412.2472.
3.22. 5-(tert-Butoxy)-3-(3-chlorophenyl)-4-(dimethylamino)-5-
oxopentyl benzoate (4n)
3.19. 5-(tert-Butoxy)-4-(dimethylamino)-5-oxo-3-(p-tolyl)pentyl
benzoate (4l)
Isolated as a 5/5 mixture of diastereomers. Colorless oil; IR
(ATR) νmax/cm-1 2975, 2936, 2870, 2833, 2790, 1715, 1598,
1573, 1474, 1452, 1432, 1391, 1367, 1314, 1269, 1144, 1113,
Isolated as a 6/4 mixture of diastereomers. Colorless oil; IR
(ATR) νmax/cm-1 2969, 2936, 2869, 2832, 2788, 1713, 1602,
1584, 1515, 1471, 1450, 1391, 1365, 1313, 1270, 1149, 1115,
1
1069, 1046, 1026, 999, 943, 878, 842, 783, 737, 710, 696; H
1
1069, 1048, 1026, 975, 961, 944, 849, 815, 788, 708; H NMR
NMR (400 MHz, CDCl3) δ 7.98-7.89 (2H, m, ArH), 7.58-7.51
(1H, m, ArH), 7.46-7.38 (2H, m, ArH), 7.25-7.14 (3H, m, ArH),
7.14-7.05 (1H, m, ArH), 4.24 (0.5H, ddd, J = 11.1, 6.2, 5.4 Hz, 1-
H), 4.17 (0.5H, ddd, J = 11.2, 6.4, 5.0 Hz, 1-H), 4.11 (0.5H, ddd,
J = 11.1, 8.3, 5.8 Hz, 1-H), 4.02 (0.5H, ddd, J = 11.2, 8.2, 5.8 Hz,
1-H), 3.32 (0.5H, d, J = 11.4 Hz, 4-H), 3.28 (0.5H, d, J = 11.6
Hz, 4-H), 3.21 (0.5H, ddd, J = 11.4, 10.6, 3.0 Hz, 3-H), 3.15
(0.5H, ddd, J = 11.6, 11.2, 3.0 Hz, 3-H), 2.61 (0.5H, dddd, J =
14.5, 8.3, 6.2, 3.0 Hz, 2-H), 2.42 (3H, s, N(CH3)2), 2.24 (3H, s,
N(CH3)2), 2.09 (0.5H, dddd, J = 14.2, 8.2, 6.4, 3.0 Hz, 2-H),
1.99-1.82 (1H, m, 2-H), 1.50 (4.5H, s, tBu), 1.16 (4.5H, s, tBu);
13C NMR (100 MHz, CDCl3) δ 169.8, 169.0, 166.4, 166.3, 143.4,
143.0, 134.3, 134.2, 132.85, 132.82, 130.2, 130.1, 129.7, 129.6,
129.5, 129.4, 128.9, 128.3, 128.1, 127.1, 127.0, 126.9, 126.5,
81.5, 80.8, 72.6, 72.5, 63.1, 62.8, 42.41, 42.38, 41.3, 41.2, 32.5,
(400 MHz, CDCl3) δ 8.00-7.91 (2H, m, ArH), 7.57-7.49 (1H, m,
ArH), 7.46-7.36 (2H, m, ArH), 7.13-7.02 (4H, m, ArH), 4.21
(0.4H, ddd, J = 10.9, 6.8, 4.8 Hz, 1-H), 4.15 (0.6H, ddd, J = 11.0,
6.9, 4.8 Hz, 1-H), 4.09 (0.4H, ddd, J = 10.9, 8.4, 6.0 Hz, 1-H),
4.00 (0.6H, ddd, J = 11.0, 8.3, 6.2 Hz, 1-H), 3.37 (0.6H, d, J =
11.2 Hz, 4-H), 3.31 (0.4H, d, J = 11.6 Hz, 4-H), 3.19 (0.6H, ddd,
J = 11.2, 11.0, 3.2 Hz, 3-H), 3.13 (0.4H, ddd, J = 11.6, 11.4, 3.2
Hz, 3-H), 2.57 (0.4H, dddd, J = 14.2, 8.4, 6.8, 3.2 Hz, 2-H), 2.42
(2.4H, s, N(CH3)2), 2.30 (1.8H, s, ArCH3), 2.28 (1.2H, s, ArCH3),
2.25 (3.6H, s, N(CH3)2), 2.07 (0.6H, dddd, J = 13.5, 8.3, 6.9, 3.2
Hz, 2-H), 1.94-1.80 (1H, m, 2-H), 1.51 (5.4H, s, tBu), 1.13
(3.6H, s, tBu); 13C NMR (100 MHz, CDCl3) δ 170.3, 169.3,
166.4, 166.3, 137.8, 137.3, 136.3, 136.0, 132.70, 132.66, 130.35,
130.30, 129.5, 129.4, 129.2, 128.9, 128.6, 128.20, 128.19, 127.9,