6
Tetrahedron
ACCEPTED MANUSCRIPT
4.2.14. (2S,4R)-4-(4-fluorophenyl)-2-phenylchroman (5c).16
4.2.20.
(1S,4R,4aR,9R,9aR)-9-phenyl-2,3,4,4a,9,9a-
Physical Appearance: white solid, 1H NMR (500 MHz, CDCl3) δ
7.48 (d, J = 7.3 Hz, 2H), 7.39 (t, J = 7.5 Hz, 2H), 7.21 – 7.12 (m,
3H), 7.04 – 6.93 (m, 4H), 6.83 – 6.77 (m, 1H), 6.74 (d, J = 7.7
Hz, 1H), 5.23 – 5.17 (m, 1H), 4.36 (dd, J = 12.2, 5.8 Hz, 1H),
2.49 – 2.35 (m, 1H), 2.27 – 2.17 (m, 1H); 13C NMR (125 MHz,
CDCl3) δ 162.85, 160.90, 155.62, 141.24, 130.14, 130.08,
129.76, 128.73, 128.24, 128.06, 126.18, 120.79, 117.24, 115.71,
115.54, 78.18, 42.90, 40.94; IR v/cm-1: 3067, 1620, 1518, 1486,
1253, 1034, 834, 755.
hexahydro-1H-1,4-methanoxanthene (5i). Physical Appearance:
white solid, H NMR (500 MHz, CDCl3) δ 7.41 (t, J = 7.4 Hz,
1
2H), 7.35 – 7.29 (m, 3H), 7.15 – 7.10 (m, 1H), 6.94 (dd, J = 7.8,
0.7 Hz, 1H), 6.84 – 6.80 (m, 1H), 6.58 – 6.54 (m, 1H), 3.95 (d, J
= 6.8 Hz, 1H), 3.49 (d, J = 10.8 Hz, 1H), 2.60 (d, J = 4.8 Hz,
1H), 2.20 – 2.12 (m, 2H), 2.07 (d, J = 2.7 Hz, 1H), 1.66 – 1.57
(m, 1H), 1.49 – 1.40 (m, 1H), 1.27 – 1.23 (m, 1H), 1.21 – 1.14
(m, 1H), 1.12 – 1.03 (m, 1H); 13C NMR (125 MHz, CDCl3) δ
156.19, 141.40, 133.28, 129.89, 128.79, 127.37, 127.03, 126.81,
122.06, 117.12, 84.96, 55.17, 44.85, 43.41, 40.53, 33.52, 29.08,
24.86; HRMS (ESI) calcd. for C20H21O, [M+H]+: 277.1592;
found: 277.1588. IR v/cm-1: 3091, 1628, 1478, 1459, 1230, 1034,
745, 701.
4.2.15. (2S,4R)-6-bromo-2,4-diphenylchroman (5d).16 Physical
1
Appearance: white solid, H NMR (500 MHz, CDCl3) δ 7.44 (d,
J = 7.3 Hz, 2H), 7.37 (t, J = 7.5 Hz, 2H), 7.34 – 7.28 (m, 5H),
7.20 – 7.16 (m, 3H), 7.12 – 7.08 (m, 1H), 6.91 – 6.85 (m, 1H),
6.82 (d, J = 8.7 Hz, 1H), 5.15 (dd, J = 11.4, 1.2 Hz, 1H), 4.28
(dd, J = 12.2, 5.8 Hz, 1H), 2.43 – 2.33 (m, 1H), 2.27 – 2.18 (m,
1H); 13C NMR (125 MHz, CDCl3) δ 154.78, 143.64, 140.82,
132.31, 130.85, 128.99, 128.71, 128.57, 128.30, 127.22, 126.14,
119.02, 112.86, 78.36, 43.49, 40.27; IR v/cm-1: 3058, 1629, 1509,
1483, 1237, 1011, 834, 754.
4.2.21.
trimethyl(((2S,4R)-4-phenylchroman-2-
yl)methyl)silane (5j). Physical Appearance: white solid, 1H NMR
(500 MHz, CDCl3) δ 7.33 – 7.29 (m, 2H), 7.22 – 7.16 (m, 2H),
7.10 (d, J = 8.2 Hz, 2H), 6.85 – 6.81 (m, 2H), 6.75 – 6.70 (m,
1H), 4.23 – 4.15 (m, 2H), 2.08 – 1.93 (m, 2H), 1.16 – 1.10 (m,
1H), 1.01 – 0.95 (m, 1H), 0.13 (s, 4H), 0.01 (s, 5H); 13C NMR
(125 MHz, CDCl3) δ 156.50, 145.93, 131.56, 129.39, 129.07,
128.28, 127.37, 126.97, 123.89, 120.90, 117.73, 70.65, 44.22,
41.07, 24.57, 0.00; HRMS (ESI) calcd. for C19H25OSi, [M+H]+:
297.1675; found: 297.1671. IR v/cm-1: 3062, 1638, 1496, 1458,
1231, 1065, 841, 751.
4.2.16. (2S,4R)-2-phenyl-4-(p-tolyl)chroman (5e).16 Physical
1
Appearance: white solid, H NMR (500 MHz, CDCl3) δ 7.48 (d,
J = 7.4 Hz, 2H), 7.38 (t, J = 7.5 Hz, 2H), 7.34 – 7.31 (m, 2H),
7.12 (d, J = 1.4 Hz, 4H), 7.02 (d, J = 8.0 Hz, 1H), 6.94 (d, J = 8.1
Hz, 1H), 6.78 (d, J = 4.1 Hz, 2H), 5.20 (d, J = 10.9 Hz, 1H), 4.32
(dd, J = 12.1, 5.8 Hz, 1H), 2.42 – 2.35 (m, 1H), 2.33 (s, 3H), 2.30
– 2.21 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 155.63, 141.58,
141.41, 136.46, 129.90, 129.48, 128.69, 128.58, 128.15, 127.83,
126.23, 120.67, 117.09, 78.28, 43.23, 40.76, 21.19; IR v/cm-1:
3065, 1633, 1505, 1481, 1266, 1234, 753, 701.
4.2.17. (2S,4R)-4-(4-methoxyphenyl)-2-phenylchroman (5f).16
Physical Appearance: white solid; 1H NMR (500 MHz, CDCl3) δ
7.48 (d, J = 7.3 Hz, 2H), 7.42 – 7.36 (m, 2H), 7.34 – 7.31 (m,
2H), 7.16 – 7.10 (m, 3H), 6.94 (d, J = 8.1 Hz, 1H), 6.87 – 6.84
(m, 2H), 6.80 – 6.76 (m, 2H), 5.21 (dd, J = 11.4, 1.4 Hz, 1H),
4.31 (dd, J = 12.2, 5.8 Hz, 1H), 3.79 (s, 3H), 2.41 – 2.34 (m, 1H),
2.29 – 2.18 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 158.59,
155.60, 141.42, 136.63, 129.86, 129.64, 128.69, 128.15, 127.83,
126.21, 120.67, 117.08, 114.20, 78.31, 55.41, 42.81, 40.83; IR
v/cm-1: 3080, 1642, 1659, 1481, 1263, 1235, 748, 696.
4.2.22. 6-methyl-2-phenylchroman (6a). Physical Appearance:
1
white solid, H NMR (500 MHz, CDCl3) δ 7.44 – 7.35 (m, 4H),
7.33 – 7.29 (m, 1H), 6.95 – 6.88 (m, 2H), 6.81 (d, J = 8.2 Hz,
1H), 5.03 (dd, J = 10.1, 2.3 Hz, 1H), 3.00-2.91 (m, 1H), 2.78 –
2.72 (m, 1H), 2.27 (s, 3H), 2.22 – 2.16 (m, 1H), 2.12 – 2.03 (m,
1H); 13C NMR (125 MHz, CDCl3) δ 153.06, 142.02, 129.99,
129.60, 128.63, 128.09, 127.90, 126.13, 121.60, 116.80, 77.83,
30.19, 25.19, 20.63; HRMS (ESI) calcd. for C16H16ONa,
[M+Na]+: 247.1099; found: 247.1094. IR v/cm-1: 3065, 1623,
1500, 1251, 1214, 945, 817, 749.
4.2.23.
2-(4-methoxyphenyl)chroman
(6b);
Physical
1
Appearance: white solid, H NMR (500 MHz, CDCl3) δ 7.35 (d,
J = 8.6 Hz, 2H), 7.10 (dd, J = 17.6, 8.3 Hz, 2H), 6.94 – 6.84 (m,
4H), 5.01 (dd, J = 10.2, 2.2 Hz, 1H), 3.82 (s, 3H), 3.05 – 2.95 (m,
1H), 2.84 – 2.77 (m, 1H), 2.21 – 2.15 (m, 1H), 2.14 – 2.05 (m,
1H); 13C NMR (125 MHz, CDCl3) δ 159.46, 155.40, 134.04,
129.65, 127.51, 121.96, 120.39, 117.08, 114.08, 77.65, 55.47,
29.96, 25.38; HRMS (ESI) calcd. for C16H16O2Na, [M+Na]+:
263.1048; found: 263.1042. IR v/cm-1: 3072, 1601, 1522, 1499,
1254, 1230, 836, 815.
4.2.18. (2S,4R)-4-phenyl-2-(p-tolyl)chroman (5g).16 Physical
1
Appearance: white solid, H NMR (500 MHz, CDCl3) δ 7.37 (d,
J = 8.0 Hz, 2H), 7.32 – 7.29 (m, 2H), 7.24 – 7.19 (m, 5H), 7.16 –
7.11 (m, 2H), 6.96 – 6.92 (m, 1H), 6.79 – 6.74 (m, 1H), 5.17 (dd,
J = 11.4, 1.5 Hz, 1H), 4.34 (dd, J = 12.1, 5.9 Hz, 1H), 2.41 – 2.36
(m, 1H), 2.35 (s, 3H), 2.32 – 2.26 (m, 1H); 13C NMR (125 MHz,
CDCl3) δ 155.77, 144.74, 138.37, 137.92, 129.91, 129.36,
128.78, 128.73, 127.86, 126.88, 126.24, 120.63, 117.15, 78.15,
43.70, 40.62, 21.31; IR v/cm-1: 3075, 1645, 1493, 1458, 1273,
1235, 756, 705.
4.2.24. 7-methyl-1,3a,9,9a-tetrahydrocyclopenta[b]chromene
(6c). Physical Appearance: white solid, 1H NMR (500 MHz,
CDCl3) δ 6.86-6.76 (m, 2H), 6.67 (d, J = 8.0 Hz, 1H), 5.88 – 5.85
(m, 1H), 5.75 – 5.72 (m, 1H), 5.13 (dd, J = 6.1, 3.9 Hz, 1H), 2.87
– 2.74 (m, 2H), 2.53 – 2.46 (m, 1H), 2.40 (dd, J = 14.2, 6.0 Hz,
1H), 2.19 (s, 3H), 2.09-2.01 (m, 1H); 13C NMR (125 MHz,
CDCl3) δ 153.97, 135.84, 130.87, 130.71, 129.14, 127.77,
127.29, 117.42, 85.33, 38.94, 37.02, 29.86, 20.84; HRMS (ESI)
calcd. for C13H15O, [M+H]+: 187.1123; found: 187.1120. IR
v/cm-1: 3089, 1630, 1619, 1513, 1248, 1043, 832, 813.
4.2.19.
(4bS,10R,10aR)-10-phenyl-4b,10,10a,11-
tetrahydroindeno[1,2-b]chromene (5h). Physical Appearance:
1
white solid, H NMR (500 MHz, CDCl3) δ 7.53 (dd, J = 9.6, 8.2
Hz, 1H), 7.35 (dd, J = 9.9, 4.4 Hz, 2H), 7.27 – 7.19 (m, 4H), 7.14
– 7.03 (m, 3H), 6.93 (d, J = 7.8 Hz, 1H), 6.83 – 6.75 (m, 2H),
5.46 (d, J = 4.7 Hz, 1H), 4.64 (d, J = 6.0 Hz, 1H), 3.06 – 2.99 (m,
1H), 2.96 – 2.89 (m, 1H), 2.45 (dd, J = 15.1, 7.0 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 156.21, 144.42, 142.46, 142.12,
129.53, 129.25, 128.58, 127.58, 126.93, 125.32, 125.13, 120.58,
117.02, 81.24, 45.82, 43.22, 33.58; HRMS (ESI) calcd. for
C22H18ONa, [M+Na]+: 321.1255; found: 321.1256. IR v/cm-1:
3078, 1629, 1486, 1458, 1251, 1224, 943, 752.
4.2.25. 3,3-dimethyl-2-(2-methylprop-1-en-1-yl)chroman (6d).
Physical Appearance: white solid, 1H NMR (500 MHz, CDCl3) δ
7.08 (t, J = 7.6 Hz, 1H), 7.01 (d, J = 7.2 Hz, 1H), 6.86 – 6.78 (m,
2H), 5.33 (d, J = 9.3 Hz, 1H), 4.46 (d, J = 9.3 Hz, 1H), 2.66 (d, J
= 16.2 Hz, 1H), 2.51 (d, J = 16.2 Hz, 1H), 1.81 (s, 3H), 1.74 (s,
3H), 0.97 (s, 3H), 0.94 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
154.00, 138.66, 129.89, 127.22, 121.78, 121.13, 120.27, 116.58,
79.76, 40.16, 31.93, 26.46, 26.32, 21.04, 18.88; HRMS (ESI)