The Journal of Organic Chemistry
Article
21.3, 13.4; HRMS (ESI) m/z found (M + Na)+, 411.2289, C27H32O2
requires (M + Na)+, 411.2295
(t, J = 8.0 Hz, 2H), 7.13−7.19 (m, 4H), 7.07−6.93 (m, 4H), 6.51−
6.48 (m, 2H), 5.52 (s, 1H), 4.20 (d, J = 11.6 Hz, 1H), 3.70 (s, 3H),
3.73−3.67 (m, 1H), 2.59−2.52 (m, 1H), 2.36 (dd, J = 17.6, 4.4 Hz,
1H), 2.10 (br s, 2H), 1.93−1.89 (m, 1H), 1.81−1.78 (m, 1H), 1.72−
1.68 (m, 1H), 1.59−1.48 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
205.7, 163.1, 145.9, 142.1, 132.2, 132.1, 131.7, 130.0, 128.0, 127.9(8),
127.9(7), 126.4(6), 126.4(5), 126.1, 112.9, 77.1, 58.2, 55.2, 41.4, 39.6,
30.7, 25.2, 23.1, 22.8; HRMS (ESI) m/ z found (M + Na)+, 461.2091,
C30H 30O3 requires (M + Na)+, 461.2087
1-((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahy-
dronaphthalen-2-yl)-3-methylbutan-1-one and 1-((1S,2R,3S)-
1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahydronaphthalen-
2-yl)-3-methylbutan-1-one (13c). White solid, mp 157.1−160.2
°C; Rf 0.3 (1:19, v/v EtOAc/hexanes); IR νmax 3461, 2928, 1682, 1493,
1
1446, 1366, 1049; H NMR (300 MHz, CDCl3) δ 7.38−7.16 (m,
10H), 5.15 (s, 1H), 3.56 (td, J = 12.0, 5.2 Hz, 1H), 3.33 (d, J = 12.0
Hz, 1H), 2.57−2.50 (m, 1H), 2.32 (dd, J = 17.6, 4.4 Hz, 1H), 2.05 (br
s, 2H), 1.85−1.65 (m, 3H), 1.50−1.39 (m, 4H), 1.31 (dd, J = 18.8, 6.8
Hz, 1H), 1.13 (dd, J = 18.8, 6.8 Hz, 1H), 0.29 (d, J = 6.8 Hz, 3H), 0.16
(d, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 217.6, 145.4,
142.3, 132.0, 131.5, 128.5, 128.1, 128.0, 126.9, 126.6, 126.1, 76.6, 64.1,
56.2, 40.4, 28.9, 30.6, 25.0, 23.0, 22.7, 22.0, 21.9, 21.4; HRMS (ESI)
m/z found (M + Na)+, 411.2292, C27H32O2 requires (M + Na)+,
411.2295
1-((1R,2S,3R)-1-(4-Chlorophenyl)-1-hydroxy-3-phenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)pentan-1-one and 1-
((1S,2R,3S)-1-(4-Chlorophenyl)-1-hydroxy-3-phenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)pentan-1-one (13h).
White solid, mp 148.3−150.3 °C; Rf 0.3 (1:19, v/v EtOAc/hexanes);
1
IR νmax 3443, 2930, 1687, 1601, 1488, 1453, 1396, 1092; H NMR
(400 MHz, CDCl3) δ 7.29−7.16 (m, 9H), 5.23 (s, 1H), 3.51 (td, J =
11.6, 5.2 Hz, 1H), 3.28 (d, J = 11.6 Hz, 1H), 2.54−2.46 (m, 1H), 2.28
(dd, J = 17.2, 4.4 Hz, 1H), 2.01 (br s, 2H), 1.79−1.61 (m, 3H), 1.45−
1.24 (m, 5H), 0.79−0.67 (m, 2H), 0.61−0.55 (m, 2H), 0.46 (t, J = 6.4
Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 218.1, 144.2, 142.0, 132.5,
132.4, 131.1, 128.6, 128.2, 128.0, 127.6, 127.0, 76.4, 64.0, 46.7, 40.5,
38.6, 30.6, 25.0, 23.9, 23.0, 22.6, 21.3 13.4; HRMS (ESI) m/z found
(M + Na)+, 445.1908, C27H31ClO2 requires (M + Na)+, 445.1905
1-((1R,2S,3R)-3-(3-Bromophenyl)-1-hydroxy-1-phenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone and 1-
((1S,2R,3S)-3-(3-Bromophenyl)-1-hydroxy-1-phenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone (13i). Clear
oil Rf 0.3 (1:9, v/v EtOAc/hexanes); IR νmax 3435, 2929, 1694, 1594,
1-((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahy-
dronaphthalen-2-yl)-2-methylbutan-1-one and 1-((1S,2R,3S)-
1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahydronaphthalen-
2-yl)-2-methylbutan-1-one (13d). White solid, mp 147.2−150.0
°C; Rf 0.3 (1:19, v/v EtOAc/hexanes); IR νmax 3433, 2930, 1675, 1600,
1
1493, 1453, 1370, 1051; H NMR (300 MHz, CDCl3) δ 7.35 (t, J =
7.2 Hz, 2H), 7.31−7.25 (m, 6H), 7.21−7.16 (m, 2H), 5.73 (s, 0.5H),
5.69 (s, 0.5H), 3.61−3.53 (m, 1H), 3.41 (d, J = 11.6 Hz, 0.5H), 3.40
(d, J = 11.6 Hz, 0.5H), 2.67−2.56 (m, 1H), 2.30 (dd, J = 17.6, 2.8 Hz,
1H), 2.06 (br s, 2H), 1.84−1.73 (m, 2H), 1.68−1.64 (m, 1H), 1.49−
1.29 (m, 4H), 0.60−0.35 (m, 2H), 0.23 (t, J = 6.8 Hz, 1.5H), 0.14 (t,
J = 7.6 Hz, 1.5 H), 0.00 (d, J = 6.8 Hz, 1.5H), −0.06 (d, J = 6.8 Hz,
1.5H); 13C NMR (100 MHz, CDCl3) δ 222.2, 221.8, 145.9, 142.0,
141.0, 132.0, 131.0, 131.8(8), 131.8(1), 128.5(4), 128.5(1), 128.4,
128.0, 127.1, 127.0, 126.6(4), 126.6(3), 77.2, 63.9, 63.5, 50.7, 50.3,
41.3(2), 41.3(0), 38.9, 38.5, 30.7, 30.6, 25.1, 25.0, 23.1, 22.9, 22.7,
22.5, 12.7, 12.0, 10.4(9), 10.4(5) eight signals overlapping or missing;
HRMS (ESI) m/z found (M + Na)+, 411.2292, C27H32O2 requires (M
+ Na)+, 411.2295
1
1566, 1475, 1446, 1357; H NMR (300 MHz, CDCl3) δ 7.44−7.32
(m, 6H), 7.27−7.24 (1H), 7.18−7.15 (m, 2H), 4.61 (s, 1H), 3.53 (td,
J = 12.0, 5.1 Hz, 1H), 3.47 (d, J = 12.0 Hz, 1H), 2.49−2.40 (m, 1H),
2.33−2.26 (m, 1H), 2.04 (br s, 2H), 1.85−1.61 (m, 3H), 1.52−1.42
(m, 3H), 1.27 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 215.4, 145.1,
145.0, 131.9, 131.7, 130.6, 130.2, 130.1, 128.2, 126.7, 125.9, 122.7,
76.4, 64.2, 40.0, 39.1, 34.3, 30.6, 35.0, 23.0, 22.6 one signal missing or
overlapping; HRMS (ESI) m/z found (M + Na)+, 447.0920,
C24H25BrO2 requires (M + Na)+, 447.0930
1-((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahy-
dronaphthalen-2-yl)-2,2-dimethylpropan-1-one and 1-
((1S,2R,3S)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahydro-
naphthalen-2-yl)-2,2-dimethylpropan-1-one (13e). White solid,
mp 187.4−190.3 °C; Rf 0.3 (1:19, v/v EtOAc/hexanes); IR νmax 3448,
2913, 1735, 1675, 1657, 1444, 1364, 1259, 1051; 1H NMR (500 MHz,
CDCl3) δ 7.38−7.37 (m, 2H), 7.30 (t, J = 7.5 Hz, 2H), 7.26−7.25 (m,
4H), 7.21−7.18 (m, 2H), 5.52 (s, 1H), 3.87 (d, J = 12.0 Hz, 1H), 3.59
(td, J = 12.0, 5.0 Hz, 1H), 2.66 (dd, J = 17.5, 14.0 Hz, 1H), 2.30 (dd,
J = 17.5, 5.0 Hz, 1H), 2.07 (br s, 2H), 1.79−1.64 (m, 3H), 1.47−1.39
(m, 3H), 0.12 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 225.8, 145.8,
142.3, 131.9, 131.8, 129.0, 128.4, 128.1, 127.1, 126.8, 126.6, 77.0, 59.4,
44.2, 41.2, 37.9, 30.6, 26.1, 25.3, 23.1, 22.7; HRMS (ESI) m/z found
(M + Na)+, 411.2291, C27H32O2 requires (M + Na)+, 411.2295
((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahy-
dronaphthalen-2-yl)(phenyl)methanone and ((1S,2R,3S)-1-Hy-
droxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)-
(phenyl)methanone (13f). White solid, mp 196.3−199.8 °C; Rf 0.3
(1:9, v/v EtOAc/hexanes); IR νmax 3448, 2935, 2915, 1643, 1447,
1355, 1223, 908; 1H NMR (400 MHz, CDCl3) δ 7.45−7.38 (m, 3H),
7.23−7.18 (m, 3H), 7.11−7.06 (m, 3H), 7.02−6.94 (m, 6H), 5.37 (s,
1H), 4.25 (d, J = 12.0 Hz, 1H), 3.70 (td, J = 12.0, 5.2 Hz, 1H), 2.61−
2.53 (m, 1H), 2.36 (dd, J = 17.6, 5.2 Hz, 1H), 2.10 (br s, 2H), 1.93−
1.89 (m, 1H), 1.82−1.77 (m, 1H), 1.72−1.67 (m, 1H), 1.62−1.50 (m,
3H); 13C NMR (100 MHz, CDCl3) δ 208.1, 145.7, 141.8, 138.9,
132.3, 132.0, 129.8, 128.2, 128.0, 127.7, 127.4, 126.9, 126.6, 126.5,
126.1, 77.2, 59.2, 41.6, 39.6, 30.8, 25.1, 23.1, 22.8; HRMS (ESI) m/z
found (M + Na)+, 431.1981, C29H28O2 requires (M + Na)+, 431.1982
((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahy-
dronaphthalen-2-yl)(4-methoxyphenyl)methanone and
((1S,2R,3S)-1-Hydroxy-1,3-diphenyl-1,2,3,4,5,6,7,8-octahydro-
naphthalen-2-yl)(4-methoxyphenyl)methanone (13g). White
solid, mp 191.8−194.3 °C; Rf 0.3 (1:9, v/v EtOAc/hexanes); IR
νmax 3435, 2930, 1634, 1599, 1571, 1493, 1453, 1352, 1263, 1228,
1175, 1026; 1H NMR (400 MHz, CDCl3) δ 7.39−7.37 (m, 2H), 7.19
1-((1R,2S,3R)-1-Hydroxy-1,3-diphenyl-2,3,4,5,6,7,8,9-octahy-
dro-1H-benzo[7]annulen-2-yl)ethanone and 1-((1S,2R,3S)-1-
Hydroxy-1,3-diphenyl-2,3,4,5,6,7,8,9-octahydro-1H-benzo[7]-
annulen-2-yl)ethanone (13j). White solid, mp 95.6−99.5 °C; Rf 0.3
(1:9, v/v EtOAc/hexanes); IR νmax 3434, 2922, 1694, 1492, 1447,
1356, 1256; 1H NMR (500 MHz, CDCl3) δ 7.39−7.19 (m, 10H), 4.77
(s, 1H), 3.47 (td, J = 12.0, 5.5 Hz, 1H), 3.40 (d, J = 12.0 Hz, 1H), 2.63
(dd, J = 18.0, 11.0 Hz, 1H), 2.41 (dd, J = 18.0, 5.0 Hz, 1H), 2.29−2.18
(m, 3H), 1.92−1.90 (m, 2H), 1.75−1.51 (m, 3H), 1.38−1.34 (m, 2H),
1.19 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 216.0, 145.7, 142.5,
138.0, 136.6, 128.6, 128.1, 127.8, 126.9, 126.7, 125.8, 78.1, 64.4, 40.9,
40.7, 35.2, 34.2, 32.2, 30.2, 27.3, 25.9; HRMS (ESI) m/z found (M +
Na)+, 383.1984, C25H28O2 requires (M + Na)+, 383.1982
1-((1R,2S,3R,4R)-1-Hydroxy-4-methyl-1,3-diphenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)pentan-1-one and 1-
((1S,2R,3S,4S)-1-Hydroxy-4-methyl-1,3-diphenyl-
1,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)pentan-1-one (13k).
White solid, mp 128.9−130.8 °C; Rf 0.3 (1:19, v/v EtOAc/hexanes);
1
IR νmax 3454, 2929, 1682, 1492, 1445, 1374, 1261, 1054, 1030; H
NMR (300 MHz, CDCl3) δ 7.39−7.17 (m, 10H), 5.10 (s, 1H), 3.42
(d, J = 12.4 Hz, 1H), 3.16 (dd, J = 12.4, 10.4 Hz, 1H), 2.57 (br s, 1H),
2.26−2.22 (m, 1H), 1.96−1.92 (m, 1H), 1.83−1.78 (m, 2H), 1.71−
1.64 (m, 1H), 1.55−1.49 (m, 1H), 1.42−1.23 (m, 5H), 0.96−0.94 (m,
2H), 0.89−0.50 (m, 4H), 0.45 (t, J = 6.4 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 218.5, 145.6, 141.9, 136.1, 131.4, 128.9, 128.5, 128.2,
126.8, 126.5, 126.1, 76.0, 63.6, 47.8, 46.5, 41.4, 28.6, 25.9, 23.8, 22.8,
+
21.3, 16.6, 13.5, 1.0; HRMS (ESI) m/z found (M + Na) , 425.2452,
C28H34O2 requires (M + Na)+, 425.2451
ASSOCIATED CONTENT
■
S
* Supporting Information
Details of computation methods used, Cartesian coordinates
and energies of optimized geometries, complete reference 15,
1122
dx.doi.org/10.1021/jo202500k | J. Org. Chem. 2012, 77, 1113−1124