The Journal of Organic Chemistry
Article
CH−OH), 7.27 (m, 2H, CHAr), 7.41−7.34 (m, 4H, CHAr), 7.75−
7.67 (m, 6H, CHAr), 7.86 (d, J = 8.4 Hz, 2H, CHAr). 13C{1H}NMR
(100 MHz, CDCl3) δ ppm: 74.4 (CH−OH), 123.0 (CHAr), 124.9
(CHAr), 125.1 (CHAr), 125.4 (CHAr), 125.8 (CHAr), 128.6
(CHAr), 128.7 (CHAr), 130.9 (CIV), 133.7 (CIV), 136.1 (CIV). MS
(ESI): 315.13 [M + H]+, 337.12 [M + Na]+. mp = 178−180 °C. meso-
5.66 (m, 2H, CHCH). 13C{1H}NMR (100 MHz, CDCl3) δ ppm:
17.8 (CH3), 17.9 (CH3), 75.6 (CH), 75.8 (CH), 128.9 (CHCH),
129.1 (CHCH), 129.4 (CHCH), 129.8 (CHCH). HRMS
(ESI): found 165.0888; calculated 165.0891 for C8H14O2Na.
(4E,8E)-Dodeca-4,8-diene-6,7-diol (dl and meso) (2n).23,17a
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Table 3, entry 14, colorless oil (194 mg, 85% yield): H NMR (400
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2h: H NMR (400 MHz, CDCl3) δ ppm: 2.25−2.00 (bs, 2H, OH),
MHz, CDCl3) δ ppm: 0.86−0.80 (m, 6H, 2 CH3), 1.37−1.31 (m, 4H,
2 CH2), 1.96 (m, 4H, 2 CH2), 2.83 (brs, 2H, OH), 3.82 (d, J = 8.4 Hz,
2H, CH−OH dl form), 4.01 (d, J = 8.4 Hz, 2H, CH−OH meso form),
5.43−5.33 (m, 2H, CHCH), 5.69−5.62 (m, 2H, CHCH). dl-2n:
13C{1H}NMR (100 MHz, CDCl3) δ ppm: 13.6 (CH3), 22.1 (CH2),
34.4 (CH2), 76.0 (CH), 128.8 (CHCH), 134.2 (CHCH). meso-
2n: 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 13.6 (CH3), 22.2
(CH2), 34.4 (CH2), 75.6 (CH), 128.0 (CHCH), 134.5 (CHCH).
HRMS (ESI): found 221.1519; calculated 221.1517 for C12H22O2Na.
(8E,12E)-Icosa-8,12-diene-10,11-diol (dl and meso) (2o).17a
Table 3, entry 15, white solid (289 mg, 81% yield): mp = 30−32 °C.
1H NMR (400 MHz, CDCl3) δ ppm: 0.82−0.79 (m, 6H, 2 CH3),
1.32−1.19 (m, 20H, 8 CH2, 2 OH, 1 H from nonequivalent CH2),
2.01−1.94 (m, 6H, 2 CH2, 1 H from nonequivalent CH2), 3.84 (dd, J
= 8.4, 1.6 Hz, 2H, CH−OH dl form), 3.99 (dd, J = 8.4, 1.6 Hz, 2H,
CH−OH meso form), 5.42−5.33 (m, 2H, CHCH), 5.70−5.64 (m,
2H, CHCH). dl-2o: 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 13.1
(CH3), 21.7 (CH2), 28.1 (CH2), 28.1 (CH2), 28.2 (CH2), 31.4 (CH2),
75.0 (CH), 127.4 (CHCH), 133.8 (CHCH). meso-2o: 13C{1H}-
NMR (100 MHz, CDCl3) δ ppm: 13.1 (CH3), 21.7 (CH2), 28.1
(CH2), 28.1 (CH2), 28.2 (CH2), 30.9 (CH2), 74.7 (CH), 126.8
(CHCH), 134.3 (CHCH). HRMS (ESI): found 333.2756;
calculated 333.2770 for C20H38O2Na.
(6E,8E,12E,14E)-Icosa-6,8,12,14-tetraene-10,11-diol (meso)
(2p).17a Table 3, entry 16, colorless oil (125 mg, 55% yield): meso-
2p: 1H NMR (400 MHz, CDCl3) δ ppm: 0.83−0.79 (m, 10H, 2 CH3,
1 CH2, 2 OH), 1.23−1.18 (m, 12H, 6 CH2), 2.00 (dd, 2H, 1 CH2),
4.10 (d, J = 8.4 Hz, 2H, CH−OH), 5.49 (dd, J = 15.6, 6.0 Hz, 2H,
CHCH), 5.65 (td, J = 14.4, 6.82 Hz, 2H, CHCH), 5.97 (dd, J =
15.2, 10.4 Hz, 2H, CHCH), 6.20 (dd, J = 15.2, 10.4 Hz, 2H, CH
CH). 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 14.0 (CH3), 22.5
(CH2), 28.8 (CH2), 31.4 (CH2), 32.6 (CH2), 75.5 (CH), 127.8
(CHCH), 129.2 (CHCH), 133.8 (CHCH), 136.5 (CH
CH). HRMS (ESI): found 329.2468; calculated 329.2457 for
C20H34O2Na.
5.95 (s, 2H, CH−OH), 7.39−7.33 (m, 4H, CHAr), 7.44 (td, J = 8.0,
1.4 Hz, 2H, CHAr), 7.57 (dd, J = 7.2, 1.2 Hz, 2H, CHAr), 7.76 (d, J =
8.2 Hz, 2H, CHAr), 7.83 (d, J = 8.0 Hz, 2H, CHAr), 7.93 (d, J = 8.0
Hz, 2H, CHAr). 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 74.2
(CH−OH), 123.1 (CHAr), 124.9 (CHAr), 125.2 (CHAr), 125.5
(CHAr), 126.0 (CHAr), 128.6 (CHAr), 128.8 (CHAr), 131.4 (CIV),
133.5 (CIV), 135.8 (CIV). MS (ESI): 315.13 [M + H]+, 337.12 [M +
Na]+. mp =179−181 °C.
1,2-Bis(4-methylphenyl)-1,2-ethanediol (dl and meso)
(2i).18a−c,19c,17a Table 3 entry 9, beige solid (223 mg, 80% yield):
mp = 161−163 °C [lit. 161−180 °C]. 1H NMR (400 MHz, CDCl3) δ
ppm: 2.22 (s, 6H, 2 CH3), 2.26 (s, 6H, 2 CH3), 4.57 (s, 2H, CH−OH
dl form), 4.65 (s, 2H, CH−OH meso form), 7.10−6.93 (m, 8H,
CHAr). 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 21.2 (4 CH3), 78.1
(CH−OH meso form), 78.8 (CH−OH dl form), 126.9 (2 CHAr),
127.1 (2 CHAr), 128.8 (2 CHAr), 129.0 (2 CHAr), 137.0 (2 CIV),
137.5 (CIV), 137.8 (CIV). MS (ESI): 243.13 [M + H]+, 267.12 [M +
Na]+.
1,2-Bis(4-methoxyphenyl)-1,2-ethanediol (dl and meso)
(2j).18b,c,19c,20a,17a Table 3 entry 10, white solid (95 mg, 30%
1
yield): mp = 165−166 °C [lit. 164−168 °C]. dl-2M: H NMR (400
MHz, CDCl3) δ ppm: 3.69 (s, 6H, CH3), 4.56 (s, 2H, CH−OH), 6.68
(dd, J = 6.8, 4.2 Hz, 4H, 2 CHAr), 6.96 (dd, J = 8.4, 5.6 Hz, 4H, 2
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CHAr). meso-2M: H NMR (400 MHz, CDCl3) δ ppm: 3.73 (s, 6H,
CH3), 4.66 (s, 2H, CH−OH), 6.78 (dd, J = 8.4, 2.0 Hz, 4H, 2 CHAr),
7.14 (dd, J = 6.8, 2.0 Hz, 4H, CHAr). 13C{1H}NMR (100 MHz,
CDCl3) δ ppm: 55.2 (OCH3), 55.3 (OCH3), 77.8 (CH meso form),
78.8 (CH dl form), 113.5 (CHAr), 113.7 (CHAr), 128.2 (CHAr),
128.3 (CHAr), 132.0 (CIV), 132.1 (CIV), 159.0 (CIV), 159.2 (CIV). MS
(ESI): 275.12 [M + H]+, 298.11 [M + Na]+.
1,2-Bis(2-methoxyphenyl)-1,2-ethanediol (dl and meso)
(2k).18b,17a Table 3 entry 11, white solid (129 mg, 41% yield): mp
= 156−158 °C. dl-2k: 1H NMR (400 MHz, CDCl3) δ ppm: 2.92 (bs,
2H, OH), 3.56 (s, 6H, CH3), 4.96 (s, 2H, CH−OH), 6.67 (d, J = 8.0
Hz, 2H, CHAr), 6.76 (td, J = 7.5, 1.2 Hz, 2H, CHAr), 7.10−7.07 (m,
2H, 2 CHAr). 13C{1H}NMR (100 MHz, CDCl3) δ ppm: 55.2
(OCH3), 74.5 (CH), 110.2 (CHAr), 120.5 (CHAr), 128.3 (CHAr),
(1E,5E)-1,6-Diphenylhexa-1,5-diene-3,4-diol (dl and meso)
(2q).18b,17a Table 3 entry 17, white solid (196 mg, 64% yield): mp =
110−112 °C [lit. 106−155 °C]. 1H NMR (400 MHz, CDCl3) δ ppm:
4.21 (dd, J = 11.4, 5.4 Hz, 2H, CH−OH dl form), 4.36 (dd, J = 9.4, 3.8
Hz, 2H, CH−OH meso form), 6.25−6.17 (m, 2H, CHCH), 6.68−
6.61 (m, 2H, CHCH), 7.33−7.22 (m, 10H, CHAr). 13C{1H}NMR
(100 MHz, CDCl3) δ ppm: 78.5 (CH), 122.2 (CIV), 128.7 (2 CHAr),
131.4 (2 CHAr), 138.4 (CIV). 13C{1H}NMR (100 MHz, CDCl3) δ
ppm: 75.8 (CH meso form), 75.9 (CH dl form), 126.6 (CH), 126.7
(CH), 127.1 (CH), 127.8 (CH), 127.9 (CH), 128.0 (CH), 128.6 (2
CH), 132.7 (CH), 133.0 (CH), 136.4 (CIV), 136.5 (CIV). MS (ESI):
267.13 [M + H]+, 289.12 [M + Na]+.
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128.4 (CIV), 128.6 (CHAr), 157.0 (CIV). meso-2k: H NMR (400
MHz, CDCl3) δ ppm: 2.92 (bs, 2H, OH), 3.60 (s, 6H, CH3), 5.17 (s,
2H, CH−OH), 6.72 (dd, J = 8.2, 1.2 Hz, 2H, CHAr), 6.81 (td, J = 7.5,
1.2 Hz, 2H, CHAr), 7.07 (dd, J = 7.5, 1.2 Hz, H, CHAr), 7.12 (td, J =
7.5, 1.2 Hz, 2H, CHAr). 13C{1H}NMR (100 MHz, CDCl3) δ ppm:
55.3 (OCH3), 73.7 (CH), 110.2 (CHAr), 120.5 (CHAr), 128.3
(CHAr), 128.5 (CHAr), 128.5 (CIV), 156.9 (CIV). MS (ESI): 275.12
[M + H]+, 298.11 [M + Na]+.
1,2-Bis(3-methoxyphenyl)-1,2-ethanediol (dl and meso)
(2l).19a,c,17a Table 3 entry 12, pale yellow solid (346 mg, 78%
yield): mp = 161−163 °C. dl-2l: 1H NMR (400 MHz, CDCl3) δ ppm:
2.39 (bs, 2H, OH), 3.62 (s, 6H, CH3), 4.56 (s, 2H, CH−OH), 6.77−
6.61 (m, 6H, CHAr), 7.06 (bt, J = 7.8 Hz, 2H, CHAr). 13C{1H}NMR
(100 MHz, CDCl3) δ ppm: 55.2 (OCH3), 78.9 (CH), 112.2 (CHAr),
113.7 (CHAr), 119.2 (CHAr), 129.2 (CHAr), 141.5 (CIV), 159.4
2,3-Diphenylbutane-2,3-diol (dl and meso) (2s).18b,20a,17a
Table 3 entry 19, white solid (111 mg, 40% yield): mp = 127−130 °C.
1H NMR (400 MHz, CDCl3) δ ppm: 1.41 (s, 6H, CH3 dl form), 1.49
(s, 6H, CH3 meso form), 2.39 (bs, 2H, OH dl and meso forms), 7.16−
7.10 (m, 10H, CHAr dl and meso forms). 13C{1H}NMR (100 MHz,
CDCl3) δ ppm: 25.0 (CH3 dl form), 25.1 (CH3 meso form), 78.7 (CIV
meso form), 78.9 (CIV dl form), 126.9 (CHAr), 127.0 (2 CHAr), 127.1
(CHAr), 127.2 (2 CHAr), 127.3 (2 CHAr), 127.4 (2 CHAr), 143.4
(CIV), 143.8 (CIV). MS (ESI): 243.13 [M + H]+, 267.12 [M + Na]+.
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(CIV). meso-2l: H NMR (400 MHz, CDCl3) δ ppm: 2.39 (bs, 2H,
OH), 3.65 (s, 6H, CH3), 4.69 (s, 2H, CH−OH), 6.77−6.61 (m, 6H,
CHAr), 7.14 (bt, J = 7.9 Hz, 2H, CHAr). 13C{1H}NMR (100 MHz,
CDCl3) δ ppm: 55.2 (OCH3), 78.0 (CH), 112.3 (CHAr), 114.0
(CHAr), 119.5 (CHAr), 129.2 (CHAr), 141.5 (CIV), 159.5 (CIV). MS
(ESI): 275.12 [M + H]+, 298.11 [M + Na]+.
ASSOCIATED CONTENT
■
(2E,6E)-Octa-2,6-diene-4,5-diol (dl and meso) (2m).22,17a
S
* Supporting Information
1
Table 3, entry 13, colorless oil (136 mg, 83% yield): H NMR (400
1H and 13C experiments spectra are provided. The Supporting
MHz, CDCl3) δ ppm: 1.66 (t, 6H, J = 6.5 Hz, CH3), 2.55−2.47 (bs,
2H, OH), 3.84 (d, 2H, J = 4.7 Hz, CH−OH, dl form), 3.99 (d, 2H, J =
6.2 Hz, CH−OH, meso form), 5.45−5.36 (m, 2H, CHCH), 5.73−
E
J. Org. Chem. XXXX, XXX, XXX−XXX