The Journal of Organic Chemistry
Article
along with 7.5% of recovered 1b, chromatography using 1:1 to 1:2 PE/
EtOAc; mp 105−106 °C. 1H NMR (400 MHz, CD3OD) δ 7.35−7.10
(m, 5H), 3.86 (dd, J = 8.0, 2.9 Hz, 1H), 3.74 (dd, J = 11.5, 2.6 Hz, 1H),
3.53 (dd, J = 12.5 Hz, 5.0 Hz, 1H), 2.78−2.62 (m, 2H), 1.93−1.76 (m,
2H), 1.21 (s, 3H); 13C{1H} NMR (100 MHz, CD3OD) δ 144.1, 129.3,
126.7, 85.7, 76.4, 63.8, 37.2, 30.5, 18.0; FT-IR (film of a concd. solution
in CH2Cl2) 3366, 3060, 3026, 2941, 1603, 1496, 1454, 1377, 1188,
1090, 1062, 1030, 903, 747, 699, 668 cm−1; ESI-MS m/z 249.2 ([M +
Na]+); ESI-HRMS calcd. for C12H18O4Na ([M + Na]+) 249.1097,
found 249.1101.
Data for (2S*,3S*)-3-Methyl-5-phenylpentane-1,2,3-triol (3b). 3b
was obtaind as a white solid, 9 mg, 14% from 1b, chromatography using
1:1 to 1:2 PE/EtOAc; mp 105−106 °C. 1H NMR (500 MHz, CD3OD)
δ 7.26−7.11 (m, 5H), 3.77 (dd, J = 10.5 Hz, 2.7 Hz, 1H), 3.59−3.51 (m,
2H), 2.69 (t, J = 8.8 Hz, 2H), 1.89−1.81 (m, 1H), 1.76−1.68 (m, 1H),
1.22 (s, 3H); 13C{1H} NMR (125 MHz, CD3OD) δ 144.2, 129.3,
126.6, 78.6, 74.8, 63.9, 41.7, 30.9, 23.0; FT-IR (film of a concd. solution
in CH2Cl2) 3391, 3025, 2927, 1602, 1496, 1454, 1375, 1061, 1029, 747,
699 cm−1; ESI-MS m/z 233.1 ([M + Na]+); ESI-HRMS calcd. for
C12H18O3Na ([M + Na]+) 233.1148, found 233.1152.
Data for 1-(1-Hydroperoxycyclohexyl)ethane-1,2-diol (2c). 2c was
obtained as a colorless oil, 49 mg, 82% from 1c, chromatography using
1:1 to 1:2 and finally 1:3 PE/EtOAc; 1H NMR (400 MHz, CDCl3) δ
9.96 (s, 1H), 4.22 (s, 2H), 3.82−3.68 (m, 3H), 1.94 (d, J = 13.8 Hz,
1H), 1.87 (d, J = 13.9 Hz, 1H), 1.69−1.44 (m, 5H), 1.38−1.14 (m,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 83.8, 75.8, 62.5, 29.6, 28.7,
25.6, 21.1, 21.0; FT-IR (film) 3373, 2936, 2862, 1448, 1154, 1076,
1018, 929, 878, 819, 739 cm−1; ESI-MS m/z 221.1 ([M + COOH]−);
ESI-HRMS calcd. for C8H16O4Cl ([M + Cl]−) 211.0743, found
211.0744.
128.44 (CH), 126.0 (CH), 89.3 (CH), 75.0 (quat), 66.3 (CH2), 32.6
(CH2), 29.4 (CH2), 21.1 (CH3) (assigned with the aid of DEPT 135);
FT-IR (film) 3348, 3085, 3062, 3026, 2935, 2864, 1603, 1496, 1454,
1382, 1244, 1115, 1041, 918, 752, 700 cm−1; ESI-MS m/z 249.2 ([M +
Na]+); ESI-HRMS calcd. for C12H18O4Na ([M + Na]+) 249.1097,
found 249.1096.
Data for (2R*,3S*)-2-Hydroperoxy-2-methyl-5-phenylpentane-
1,3-diol (2e′). 2e was obtained as a colorless oil, 14 mg, 18% from
1e, chromatography using first 2:3, then 1:1 PE/EtOAc, and finally
1
EtOAc; H NMR (500 MHz, CDCl3) δ 9.34 (s, 1H), 7.30−7.17 (m,
5H), 3.91−3.84 (m, 2H), 3.78 (d, J = 12.7 Hz, 1H), 3.46 (br s, 2H),
2.97 (ddd, J = 13.7, 9.8 Hz, 4.9 Hz, 1H), 2.66 (ddd, J = 13.9, 9.3, 7.3 Hz,
1H), 1.90−1.74 (m, 2H), 1.07 (s, 3H); 13C{1H} NMR (125 MHz,
CDCl3) δ 141.7 (quat), 128.53 (CH), 128.47 (CH), 126.0 (CH), 85.8
(quat), 74.0 (CH), 64.7 (CH2), 33.5 (CH2), 32.7 (CH2), 16.4 (CH3)
(assigned with the aid of DEPT 135); FT-IR (film) 3365, 3086, 3062,
3026, 2929, 2860, 1603, 1496, 1454, 1376, 1257, 1223, 1044, 933, 751,
700 cm−1; ESI-MS m/z 249.1 ([M + Na]+); ESI-HRMS calcd. for
C12H18O4Na ([M + Na]+) 249.1097, found 249.1094.
Data for (2R*,3S*)-2-Methyl-5-phenylpentane-1,2,3-triol (3e). 3e
was obtained as a colorless oil, 19 mg, 30% from 1e, chromatography
using first 2:3, then 1:1 PE/EtOAc, and finally EtOAc; 1H NMR (400
MHz, CD3OD) δ 7.26−7.11 (m, 5H), 3.56 (d, J = 11.0 Hz, 1H), 3.51
(dd, J = 10.6, 1.3 Hz, 1H), 3.44 (d, J = 11.1 Hz, 1H), 2.91 (ddd, J = 13.4,
10.5, 4.6 Hz, 1H), 2.61 (ddd, J = 13.5, 10.0, 7.0 Hz, 1H), 2.02−1.93 (m,
1H), 1.69−1.59 (m, 1H), 1.08 (s, 3H); 13C{1H} NMR (100 MHz,
CD3OD) δ 143.8, 129.5, 129.3, 126.7, 75.6, 75.3, 68.8, 34.01, 34.00,
19.0; FT-IR (film) 3406, 3085, 3062, 3026, 2927, 1603, 1496, 1454,
1381, 1257, 1044, 941, 833, 750, 700 cm−1; ESI-MS m/z 233.2 ([M +
Na]+); ESI-HRMS calcd. for C12H18O3Na ([M + Na]+) 233.1148,
found 233.1150. (note that 3e = 3h.)
Data for (3R*,4S*)-8-(Benzyloxy)-2-hydroperoxy-2-methyloc-
tane-3,4-diol (2f). 2f was obtained as a colorless oil, 49 mg, 72%
from 1f, chromatography using 1:1 PE/EtOAc; 1H NMR (400 MHz,
CDCl3) δ 9.98 (s, 1H), 7.36−7.25 (m, 5H), 4.49 (s, 2H), 3.82 (dd, J =
7.5, 4.2 Hz, 1H), 3.49 (t, J = 6.3 Hz, 2H), 3.42−3.28 (m, 2H), 2.62 (br s,
1H), 1.74−1.59 (m, 3H), 1.57−1.38 (m, 3H), 1.29 (s, 3H), 1.23 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 138.1, 128.3, 127.7, 127.6,
84.8, 76.7, 72.9, 70.1, 69.4, 34.9, 29.3, 22.5, 20.9; FT-IR (film) 3388,
3092, 3059, 3030, 2980, 2939, 2863, 2798, 1603, 1496, 1454, 1365,
1206, 1151, 1100, 1074, 1028, 911, 737, 698 cm−1; ESI-MS m/z 321.2
([M + Na]+); ESI-HRMS calcd. for C16H26O5Na ([M + Na]+)
321.1673, found 321.1672.
Data for 1-(1-Hydroxycyclohexyl)ethane-1,2-diol (3c). 3c was
obtained as a white solid, 6 mg, 11% from 1c, chromatography using 1:1
1
to 1:2 and finally 1:3 PE/EtOAc; mp 111−112 °C. H NMR (400
MHz, CD3OD) δ 3.78 (dd, J = 11.3, 3.3 Hz, 1H), 3.55 (dd, J = 11.1, 7.8
Hz, 1H), 3.36 (dd, J = 8.0, 3.2 Hz, 1H), 1.71−1.43 (m, 9H), 1.29−1.18
(m, 1H); 13C{1H} NMR (100 MHz, CD3OD) δ 79.0, 74.0, 63.6, 34.6,
33.5, 27.0, 22.52, 22.48; FT-IR (film of a concd. solution in CH2Cl2)
3307, 2930, 2856, 1446, 1400, 1337, 1263, 1090, 1063, 1023, 971, 908,
879 cm−1; ESI-MS m/z 183.1 ([M + Na]+); ESI-HRMS calcd. for
C8H16O3Na ([M + Na]+) 183.0992, found 183.0998.
Data for (2R*,3S*)-3-Hydroperoxyheptane-1,2-diol (2d). 2d was
obtained as a colorless oil, 28 mg, 60% from 1d, chromatography using
1
1:1 to 1:2, then 1:3 PE/EtOAc, and finally MeOH; H NMR (500
Data for (3R*,4S*)-8-(Benzyloxy)-2-methyloctane-2,3,4-triol (3f).
3f was obtained as a colorless oil, 7 mg, 11% from 1f, chromatography
using 1:1 PE/EtOAc; 1H NMR (400 MHz, CDCl3) δ 7.36−7.27 (m,
5H), 4.50 (s, 2H), 3.98−3.92 (m, 1H), 3.49 (t, J = 6.4 Hz, 2H), 3.13−
3.08 (m, 1H), 3.01−2.72 (m, 3H), 1.73−1.61 (m, 3H), 1.59−1.40 (m,
3H), 1.28 (s, 3H), 1.27 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ
138.4, 128.4, 127.7, 127.6, 76.4, 74.1, 72.9, 71.2, 70.2, 34.1, 29.5, 27.3,
26.2, 22.4; FT-IR (film) 3417, 3087, 3064, 3030, 2930, 2857, 2794,
1603, 1496, 1454, 1365, 1307, 1162, 1101, 1028, 949, 804, 736, 698
cm−1; ESI-MS m/z 305.2 ([M + Na]+); ESI-HRMS calcd. for
C16H26O4Na ([M + Na]+) 305.1723, found 305.1725.
MHz, CD3OD) δ 3.86 (q, J = 5.4 Hz, 1H), 3.77 (q, J = 5.1 Hz, 1H), 3.66
(dd, J = 11.3, 4.3 Hz, 1H), 3.58 (dd, J = 11.3, 6.8 Hz, 1H), 1.66−1.48
(m, 3H), 1.44−1.31 (m, 3H), 0.93 (t, J = 7.0 Hz, 3H); 13C{1H} NMR
(100 MHz, CD3OD) δ 86.9, 73.3, 64.6, 29.2, 28.6, 23.8, 14.4; FT-IR
(film) 3348, 2957, 2933, 2873, 1466, 1380, 1215, 1066, 988, 881 cm−1;
ESI-MS m/z 209.1 ([M + COOH]−); ESI-HRMS calcd. for
C7H16O4Na ([M + Na]+) 187.0941, found 187.0932.
Data for (2R*,3S*)-Heptane-1,2,3-triol (3d). 3d was obtained as a a
white solid, 9 mg, 20% from 1d, chromatography using first 1:1, then
1
1:2, and finally 1:3 PE/EtOAc and finally MeOH; mp 76−78 °C. H
NMR (400 MHz, CD3OD) δ 3.72 (dd, J = 11.2, 3.6 Hz, 1H), 3.56 (dd, J
= 11.2, 6.6 Hz, 1H), 3.52−3.41 (m, 2H), 1.72−1.64 (m, 1H), 1.58−
1.48 (m, 1H), 1.44−1.29 (m, 4H), 0.94 (t, J = 7.1 Hz, 3H); 13C{1H}
NMR (100 MHz, CD3OD) δ 76.3, 73.6, 64.7, 33.8, 29.1, 23.9, 14.5; FT-
IR (film of a concd. solution in CH2Cl2) 3260, 2953, 2938, 2914, 2872,
2856, 1487, 1458, 1439, 1315, 1083, 1042, 1005, 962, 888, 875, 730
cm−1; EI-MS m/z (%) 69 (100), 87 (62), 44 (33), 117 ([M −
CH2OH]+, 13), 147 ([M − H]+, 0.97); ESI-HRMS calcd. for C6H13O2
([M − CH2OH]+) 117.0916, found 117.0919.
Data for (3S*,4R*)-5-Hydroperoxy-5-methyl-1-phenylhexane-
3,4-diol (2g). 2g was obtained as a colorless oil, 53 mg, 74% from 1g,
1
chromatography using 2:1 to 3:2 PE/EtOAc; H NMR (400 MHz,
CDCl3) δ 9.80 (s, 1H), 7.29−7.14 (m, 5H), 3.86 (dd, J = 8.0, 5.3 Hz,
1H), 3.44 (s, 1H), 3.35 (s, 1H), 3.22 (s, 1H), 2.81−2.64 (m, 2H),
2.07−1.97 (m, 1H), 1.88−1.78 (m, 1H), 1.30 (s, 3H), 1.21 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 141.5, 128.39, 128.34, 125.9, 85.0,
76.7, 69.1, 36.8, 32.0, 22.4, 20.8; FT-IR (film) 3420, 3086, 3063, 3026,
2981, 2939, 2861, 1603, 1496, 1454, 1383, 1234, 1145, 1099, 1045, 997,
775, 748, 700 cm−1; ESI-MS m/z 263.2 ([M + Na]+); ESI-HRMS calcd.
for C13H20O4Na ([M + Na]+) 263.1254, found 263.1256.
Data for (3R*,4S*)-2-Methyl-6-phenylhexane-2,3,4-triol (3g). 3g
was obtained as a colorless oil, 16 mg, 24% from 1g, chromatography
using 2:1 to 3:2 PE/EtOAc; 1H NMR (400 MHz, CDCl3) δ 7.33−7.19
(m, 5H), 4.01 (dd, J = 8.0, 5.2 Hz, 1H), 3.37−3.04 (m, 4H), 2.83−2.67
(m, 2H), 2.07−1.97 (m, 1H), 1.91−1.81 (m, 1H), 1.31 (s, 3H), 1.27 (s,
Data for (2R*,3S*)-3-Hydroperoxy-2-methyl-5-phenylpentane-
1,2-diol (2e). 2e was obtained as a colorless oil, 20 mg, 38% from 1e,
chromatography using first 2:3, then 1:1 PE/EtOAc, and finally EtOAc;
1H NMR (400 MHz, CDCl3) δ 10.41 (br s, 1H), 7.30−7.15 (m, 5H),
3.90 (dd, J = 10.8, 2.3 Hz, 1H), 3.78 (d, J = 11.8 Hz, 1H), 3.66 (br s,
1H), 3.41 (d, J = 11.8 Hz, 1H), 2.97 (ddd, J = 13.6, 9.6, 4.8 Hz, 1H),
2.71 (dt, J = 13.6, 8.1 Hz, 1H), 1.94−1.74 (m, 2H), 1.06 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ 141.6 (quat), 128.49 (CH),
F
J. Org. Chem. XXXX, XXX, XXX−XXX