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M. Dönges et al. / Journal of Inorganic Biochemistry xxx (2015) xxx–xxx
5:1 (v/v). 2-(rel-(2R,3R)-2,3-diphenyltetrahydrofuran-5-yl)propan-2-ol
cis-(2e). Yield: 57.0 mg (202 μmol, 20%), colorless oil. Rf = 0.56
[pentane/acetone = 5:1 (v/v)]. 1H NMR (CDCl3, 400 MHz) δ 1.34
(s, 3H), 1.42 (s, 3H), 2.06–2.15 (s, 1H, OH), 2.30–2.38 (m, 2H), 3.90
(q, J = 8.8 Hz, 1H), 3.97 (dd, J = 9.8, 6.2 Hz, 1H), 5.29 (d, J = 8.8 Hz,
1H), 6.87–7.33 (m, 10H). 13C NMR (CDCl3, 101 MHz) δ 25.0, 28.0, 33.5,
50.1, 71.1, 84.4, 85.7, 126.0, 126.2, 126.8, 127.5, 127.6, 128.6, 140.0,
140.2. Mass spectrometry (MS) [70 eV, electron impact (EI)] m/z (%)
280 (1), 264 (18), 247 (4), 223 (15), 205 (19), 193 (25), 180 (100),
173 (21), 165 (17), 158 (14), 143 (34), 128 (19), 115 (59), 105 (80),
91 (46), 77 (49), 70 (24), 59 (52), 51 (15). High resolution mass spec-
trometry (HRMS) calcd. for C19H22O2 282.1620; found 282.1605. 2-
(rel-(2R,3R)-2,3-diphenyltetrahydrofuran-5-yl)propan-2-ol trans-(2e).
Yield: 91.0 mg (322 μmol, 32%), colorless oil. Rf = 0.56 [pentane/
acetone = 5:1 (v/v)]. 1H NMR (CDCl3, 400 MHz) δ 1.25 (s, 3H),
1.36 (s, 3H), 2.06–2.15 (s, 1H, OH), 2.22–2.30 (m, 1H), 2.49 (dt,
Jd = 13.0 Hz, Jt = 7.8 Hz, 1H), 3.78 (ddd, J = 7.5, 6.1, 3.8 Hz, 1H),
4.42 (t, J = 7.7 Hz, 1H), 5.39 (d, J = 5.9 Hz, 1H), 6.87–7.33
(m, 10 H). 13C NMR (CDCl3, 101 MHz) δ 24.1, 27.0, 33.9, 50.9,
72.8, 85.1, 85.3, 126.1, 126.7, 127.5, 127.8, 128.2, 128.5, 139.5,
140.5. MS (70 eV, EI) m/z (%) 280 (1), 264 (11), 247 (3), 223 (9),
205 (20), 193 (18), 180 (100), 173 (14), 165 (14), 158 (13), 143
(24), 128 (17), 115 (45), 105 (39), 91 (34), 77 (26), 72 (30), 59
(40), 51 (8). HRMS calcd. for C19H22O2–H2O 264.1514; found
264.1502. rel-(3S,5R,6R)-2,2-dimethyl-5,6-diphenyltetrahydro-2H-
pyran-3-ol rel-(3S,5R,6R)-(5e). Yield: 12.9 mg (45.7 μmol, 5%), col-
orless oil. Rf = 0.56 [pentane/acetone = 5:1 (v/v)]. 1H NMR (CDCl3,
400 MHz) δ 1.37 (s, 3H), 1.50 (s, 3H), 2.06–2.15 (m, 1H, OH), 2.03
(ddd, J = 13.1, 4.9, 3.0 Hz, 2H), 3.46 (dt, Jd = 5.5 Hz, Jt = 2.8 Hz,
1H), 3.84 (dd, J = 12.1, 4.8 Hz, 1H), 5.13 (d, J = 3.1 Hz, 1H),
6.87–7.33 (m, 10 H). MS (70 eV, EI) m/z (%) 282 (1) [M+], 264
(4), 247 (3), 222 (2), 205 (1), 193 (9), 178 (60), 165 (14), 152
(4), 143 (9), 133 (11), 115 (17), 105 (25), 91 (17), 77 (18), 72
(100), 57 (11), 51 (7). HRMS calcd. for C19H22O2 282.1620; found
282.1625. 3-(3,3-dimethyloxiran-2-yl)-1,2-diphenylpropan-1-one.
Yield: 10.7 mg (38.2 μmol, 4%), colorless oil. Rf = 0.56 [pentane/acetone =
5:1 (v/v)]. 1H NMR (CDCl3, 400 MHz) δ 1.27 (s, 3H), 1.35 (s, 3H),
2.22–2.30 (m, 1H), 3.06 (dd, J = 15.1, 9.8 Hz, 1H), 3.19 (dd, J = 15.1,
9.4 Hz, 1H), 4.56 (t, J = 9.6 Hz, 1H), 6.87–7.33 (m, 10H). MS (70 eV, EI)
m/z (%) 280 (33), 262 (22), 247 (83), 220 (28), 203 (7), 191 (27), 178
(17), 165 (14), 157 (7), 141 (8), 129 (6), 115 (31), 105 (100), 91 (13),
77 (45), 59 (12), 51 (8). HRMS calcd. for C19H20O2 280.1463; found
280.1469.
4.4.6. Oxidizing rel-(1R,2S)-5-methyl-1,2-diphenylhex-4-en-1-ol
rel-(1R,2S)-(1e) in dimethyl carbonate
Reactants: rel-(1R,2S)-5-methyl-1,2-diphenylhex-4-en-1-ol rel-
(1R,2S)-(1e) (266 mg, 1.00 mmol) in dimethyl carbonate (3 ml),
VO(L2)(OEt) (3c) (28.4 mg, 50.8 μmol, 5 mol%), and TBHP (270 μl,
5.5 M solution in nonane, 1.49 mmol) in dimethyl carbonate (3 ml).
Reaction time: 24 h at 20 °C. Eluent used for chromatographic pu-
rification: pentane/acetone = 5:1 (v/v). 2-(rel-(2S,3R,5R)-4,5-
diphenyltetrahydrofuran-2-yl)propan-2-ol rel-(2S,3R,5R)-2e. Yield:
241 mg (853 μmol, 85%), colorless solid. For spectroscopic data,
refer to Section 4.4.5.
4.4.7. Conversion of (E)-5,9-dimethyl-1-phenyldeca-4,8-dien-1-ol (E)-(1f)
Reactants: (E)-5,9-dimethyl-1-phenyldeca-4,8-dien-1-ol (E)-(1f)
(258 mg, 1.00 mmol) in chloroform (3 ml), VO(L2)(OEt) (3c)
(56.0 mg, 100 μmol, 10 mol%), and TBHP (540 μl, 5.5 M solution in
nonane, 2.97 mmol) in chloroform (3 ml). Reaction time: 48 h at
20 °C. Eluent used for chromatographic purification: pentane/acetone =
10:1 (v/v). 6-methyl-2-(rel-(2S,5R)-5-phenyltetrahydrofuran-2-yl)hept-
5-en-2-ol cis-(2f). Yield: 44.8 mg (163 μmol, 16%), colorless oil. Rf =
0.54 [pentane/acetone = 5:1 (v/v)]. 1H NMR (CDCl3, 400 MHz) δ 1.29
(s, 3H), 1.46 (ddd, J = 13.7, 11.4, 5.8 Hz, 1H), 1.63 (s, 3H), 1.70
(s, 3H), 1.77–1.85 (m, 1H), 1.91–2.13 (m, 6H), 2.31 (dddd, J = 12.2,
8.6, 6.7, 5.5 Hz, 1H), 3.89 (t, J = 7.5 Hz, 1H), 4.86 (dd, J = 8.2, 7.0 Hz,
1H), 5.14 (tt, J = 7.1, 1.3 Hz, 1H), 7.27–7.30 (m, 1H), 7.32–7.36
(m, 4H). 13C NMR (CDCl3, 101 MHz) δ 17.7, 22.1, 24.0, 25.7, 25.9, 34.2,
37.7, 73.2, 80.8, 85.6, 124.5, 125.9, 127.4, 128.4, 131.7, 142.4. MS
(70 eV, EI) m/z (%) 256 (11), 238 (10), 223 (5), 213 (13), 195 (5), 187
(34), 174 (25), 165 (6), 155 (7), 147 (21), 136 (11), 129 (23), 117
(44), 115 (44), 105 (82), 91 (100), 77 (64), 69 (54), 63 (7), 55 (18),
51 (18). Anal. calcd. for C18H26O2 (274.40): C, 78.79; H, 9.55. Found: C,
79.05; H, 9.46. 2-{(rel-2′S,5′R)-
tetrahydro-5′-[(rel-2R,5R)-5-tetrahydro-5-phenylfuran-2-yl]-5′-
(methylfuran-2′-yl)propan-2-ol trans-(6). Yield: 69.9 mg (241 μmol,
24%), colorless oil. Rf = 0.49 [pentane/acetone = 5:1 (v/v)]. 1H
NMR (CDCl3, 400 MHz) δ 1.09 (s, 3H), 1.23 (s, 3H), 1.24 (s, 3H),
1.64 (ddd, J = 12.1, 8.4, 6.7 Hz, 1H), 1.69–1.80 (m, 2H), 1.90–2.10
(m, 4H), 2.19–2.27 (m, 1H), 2.28–2.36 (m, 1H), 3.80 (t, J = 7.0 Hz,
1H), 3.98 (t, J = 7.6 Hz, 1H), 4.79 (t, J = 7.4 Hz, 1H), 7.22–7.27 (m,
1H), 7.29–7.36 (m, 4H). 13C NMR (CDCl3, 101 MHz) δ 24.2, 24.8,
25.7, 26.4, 27.7, 32.4, 34.4, 71.5, 81.0, 84.7, 85.1, 85.4, 125.7, 127.3,
128.4, 142.2. MS (70 eV, EI) m/z (%) 272 (18), 231 (9), 187 (22),
171 (8), 155 (7), 143 (88), 125 (68), 117 (59), 115 (54), 105 (35),
91 (100), 77 (43), 69 (17), 67 (20), 59 (30), 55 (24). Anal. calcd. for
C
18H26O3 (290.40): C, 74.45; H, 9.02. Found: C, 74.36; H, 9.08. 2-
4.4.5. Conversion of rel-(1R,2S)-5-methyl-1,2-diphenylhex-4-en-1-ol
rel-(1R,2S)-(1e)
{(rel-2′S,5′R)-
tetrahydro-5′-[(rel-2S,5R)-5-tetrahydro-5-phenylfuran-2-yl]-
5′(-methylfuran-2′-yl)propan-2-ol cis-(6). Yield: 39.5 mg (136 μmol,
14%), colorless oil. Rf = 0.45 [pentane/acetone = 5:1 (v/v)]. 1H NMR
(CDCl3, 400 MHz) δ 1.13 (s, 3H), 1.23 (s, 3H), 1.27 (s, 3H), 1.71–1.82
(m, 3H), 1.83–1.94 (m, 3H), 1.97–2.11 (m, 1H), 2.21 (s, 1H, OH),
2.23–2.32 (m, 1H), 3.86 (dd, J = 9.0, 6.4 Hz, 1H), 4.03 (t, J = 7.2 Hz,
Reactants: rel-(1R,2S)-5-methyl-1,2-diphenylhex-4-en-1-ol rel-
(1R,2S)-(1e) (266 mg, 1.00 mmol) in chloroform (3 ml), VO(L2)(OEt)
(3c) (28.0 mg, 50.0 μmol, 5 mol%), and TBHP (270 μl, 5.5 M solution in
nonane, 1.49 mmol) in chloroform (3 ml). Reaction time: 24 h at
20 °C. Eluent used for chromatographic purification: pentane/acetone =
5:1 (v/v). 2-(rel-(2S,3R,5R)-2,3-diphenyltetrahydrofuran-5-yl)propan-2-
ol rel-(2S,3R,5R)-(2e). Yield: 251 mg (889 μmol, 89%), colorless solid,
mp 58 °C. Rf = 0.52 [pentane/acetone = 5:1 (v/v)]. 1H NMR (CDCl3,
1H), 4.89 (t, J = 7.5 Hz, 1H), 7.24–7.28 (m, 1H), 7.29–7.36 (m, 4H). 13
C
NMR (CDCl3, 101 MHz) δ 24.0, 24.1, 26.3, 27.3, 27.8, 34.4, 34.8, 70.5,
81.2, 84.6, 85.2, 87.1, 125.9, 127.2, 128.2, 143.1. MS (70 eV, EI) m/z (%)
272 (19), 187 (24), 171 (11), 155 (10), 143 (100), 125 (75), 117 (42),
115 (44), 105 (35), 91 (65), 77 (36), 69 (16), 67 (11), 59 (11), 55 (18).
Anal. calcd. for C18H26O3 (290.40): C, 74.45; H, 9.02. Found: C, 74.68; H,
8.94. 6-methyl-2-(rel-(2R,5R)-5-phenyltetrahydrofuran-2-yl)hept-5-en-2-
ol trans-(2f). Yield: 15.5 mg (56.5 μmol, 6%), colorless oil. Rf = 0.43
[pentane/acetone = 5:1 (v/v)]. 1H NMR (CDCl3, 400 MHz) δ 1.21
(s, 3H), 1.40 (ddd, J = 13.6, 9.2, 7.4 Hz, 1H), 1.59 (s, 3H), 1.61–1.65
(m, 2H), 1.66 (s, 3H), 1.67–1.71 (m, 1H), 1.78–1.88 (m, 1H), 1.92–2.01
(m, 1H), 2.02–2.11 (m, 2H), 2.21 (s, 1H, OH), 2.76 (dd, J = 6.8, 5.9 Hz,
1H), 4.71 (t, J = 6.3 Hz, 1H), 5.06 (tt, J = 7.1, 1.2 Hz, 1H), 7.27–7.30
(m, 1H), 7.32–7.38 (m, 4H). 13C NMR (CDCl3, 101 MHz) δ 16.4, 17.6,
400 MHz) δ 1.29 (s, 3H), 1.36 (s, 3H), 2.14 (s, 1H, OH), 2.22 (dt, Jd
=
13.0 Hz, Jt = 8.5 Hz, 1H), 2.52 (ddd, J = 13.0, 9.9, 6.5 Hz, 1H), 3.19 (q,
J = 9.0 Hz, 1H), 4.17 (dd, J = 8.5, 6.6 Hz, 1H), 4.84 (d, J = 9.0 Hz, 1H),
7.14–7.21 (m, 4H), 7.21–7.32 (m, 6H). 13C NMR (CDCl3, 101 MHz) δ
24.6, 27.0, 36.2, 53.7, 71.8, 85.3, 88.1, 126.1, 126.7, 127.7, 127.8, 128.3,
128.6, 140.2, 141.0. MS (70 eV, EI) m/z (%) 264 (17), 247 (4), 223 (8),
205 (19), 193 (32), 180 (100), 173 (15), 165 (20), 158 (18), 143 (37),
128 (19), 115 (70), 105 (67), 91 (50), 77 (47), 59 (50), 51 (18). HRMS
calcd. for C19H22O2 282.1620; found 282.1603. Anal. calcd. for
C19H22O2 (282.38): C, 80.82; H, 7.85. Found: C, 80.52; H, 7.89.
Please cite this article as: M. Dönges, et al., Activating tert-butyl hydroperoxide by chelated vanadates for stereoselectively preparing