H. Göksu et al. / Journal of Molecular Catalysis A: Chemical 378 (2013) 142–147
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rac-cyclopentane-1,2/3-triol (4b): 1H NMR (400 MHz, D2O, ppm):
ı = 3.98–3.95 (m, 2 H), 3.64 (m, 1 H), 1.99–1.85 (m, 2 H), 1.43–1.23
(m, 2 H). 13C NMR (100 MHz, D2O, ppm): ı = 78.9, 75.7, 71.7, 28.4,
27.7. IR (KBr, cm−1): 3366.9, 2938.1, 1569.1, 1410.5.
3080.6, 2953.3, 2927.1, 2876.9, 1676.4, 1625.5, 1446.7, 1242.7,
1217.9, 1063.0, 1038.1.
rac-7-oxabicyclo[4.1.0]heptane-2,3,4-triol (10c): 1H NMR
(400 MHz, D2O, ppm): ı = 3.83–3.78 (m, 2 H), 3.58 (q, 1 H,
J = 5.8 Hz), 3.41 (m, 1 H), 3.08 (m, 1 H)), 2.21 (d, 1 H, J = 5.8 Hz), 1.91
(ddd, 1 H, J = 14.7, 10.1, 2.2 Hz). 13C NMR (100 MHz, D2O, ppm):
70.0, 67.6, 64.9, 55.2, 54.9, 26.5. IR (KBr, cm−1): 2931.5, 1367.1,
1223.3, 1034.9.
rac-3-hydroperoxycyclohex-1-ene (5a): 1H NMR (400 MHz,
CDCl3, ppm): ı = 9.03 (bs, 1 H), 5.94 (m, 1 H), 5.69 (m, 1 H), 4.43 (m,
1 H), 2.05–1.47 (m, 6 H). 13C NMR (100 MHz, CDCl3, ppm): ı = 134.4,
124.3, 78.6, 26.5, 25.4, 18.5. IR (KBr, cm−1): 3366.4, 2934.3, 1650.6,
1392.5, 1066.3, 944.8.
rac-cyclohexane-1,2/3-triol (5b): 1H NMR (400 MHz, D2O, ppm):
ı = 3.96 (m, 1 H), 3.73 (m, 1 H), 3.33 (m, 1 H), 1.89–1.23 (m, 6 H).
13C NMR (100 MHz, D2O, ppm): ı = 76.0, 71.0, 69.9, 31.6, 30.4, 18.3.
IR (KBr, cm−1): 3366.7, 2937.8, 1574.2, 1069.4.
The zeolite-Os0 catalyst was prepared by using our established
procedure and characterized by using many advanced techniques
[20]. In a typical procedure for the synthesis of zeolite-Os0, ion-
then followed by the reduction of Os3+ ions within the cages of zeo-
lite with excess NaBH4 in aqueous solution. The cation sites left by
Os3+ ions upon reduction are re-occupied by the sodium cations
zeolite-Os0 catalyst was determined by the inductively coupled
plasma optical emission spectroscopy (ICP-OES) as 2.1 wt% that
is used for the calculation of Os loading in all the catalytic reac-
tions.
Table 1 gives the list of cyclic or linear allylic hydroperoxides,
which were prepared by photooxygenation of the correspond-
and co-oxidant. All of the allylic hydroperoxides were iden-
tified by 1H and 13C NMR spectroscopy in comparison with
the literature data. All of the allylic hydroperoxides given in
Table 1 were reacted in acetone/water (v/v = 4/1) mixture at
room temperature in the presence of zeolite-Os0 catalyst and
without using any co-oxidant (H2O2, tBuOOH, NMO, etc.). The
products of the catalytic reactions were characterized by 1H
taken after the catalytic reactions shows that both the cyclic
or linear allylic hydroperoxides were successfully converted to
the corresponding 1,2/3-triols with the high chemical yields
and selectivity (Table 1, entries 1–11). For example, the lin-
and rac-3-hydroperoxybut-1-ene (3a) were converted to the
rac-2,3-dimethylbutane-1,2,3-triol (1b) (83%), rac-2-isopropyl-
propane-1,2,3-triol (2b) (87%) and rac-butane-1,2,3-triol (3b)
(85%), respectively (Table 1, entries 1–3). The cyclic allylic
hydroperoxides: the rac-3-hydro peroxycyclopent-1-ene (4a),
hept-1-ene (6a) and (Z)-rac-3-hydroperoxy-cyclooct-1-ene (7a)
were yielded to the rac-cyclopentane-1,2/3-triol (4b) (91%), rac-
cyclohexane-1,2/3-triol (5b) (93%), rac-cycloheptane-1,2/3-triol
(6b) (87%), and rac-cyclooctane-1,2/3-triol (7b) (75%), respectively
(Table 1, entries 4–7).
rac-3-hydroperoxycyclohept-1-ene (6a): 1H NMR (400 MHz,
CDCl3, ppm): ı = 9.21 (bs, 1 H), 5.79–5.71 (m, 2 H), 4.57 (m, 1 H),
2.14–1.31 (m, 8 H). 13C NMR (400 MHz, CDCl3, ppm): ı = 132.7,
132.6, 85.3, 30.9, 28.6, 26.8, 26.6. IR (KBr, cm−1): 3374.8, 2928.3,
1651.9, 1446.7, 1003.6, 835.6.
rac-cycloheptane-1,2/3-triol (6b): 1H NMR (400 MHz, D2O, ppm):
ı = 3.82 (m, 1 H), 3.54 (m, 1 H), 3.47 (dd, 1 H, J = 7.0, 2.6 Hz), 1.62–1.28
(m, 8 H). 13C NMR (100 MHz, D2O, ppm): 78.7, 73.9, 71.9, 32.1, 29.5,
23.3, 22.7. IR (KBr, cm−1): 3398.9, 2924.4, 1654.6, 1377.9.
rac-3-hydroperoxycyclooct-1-ene (7a): 1H NMR (400 MHz,
CDCl3, ppm): ı = 8.55 (bs, 1 H), 5.72 (m, 1 H), 5.63 (m, 1 H), 4.93
(m, 1 H), 2.22–1.32 (m, 10 H). 13C NMR (100 MHz, CDCl3, ppm):
ı = 131.6, 130.7, 83.5, 33.0, 29.0, 26.6, 26.3, 23.6. IR (KBr, cm−1):
3390.6, 2928.9, 1653.8, 1451.1, 1040.2, 754.3.
rac-cyclooctane-1,2/3-triol (7b): 1H NMR (400 MHz, D2O, ppm):
ı = 3.87 (m, 1 H), 3.64 (m, 1 H), 3.51 (m, 1 H), 1.58–1.24 (m, 10 H).
13C NMR (100 MHz, D2O, ppm): 78.0, 72.9, 70.5, 32.3, 30.2, 25.9,
25.4, 22.6. IR (KBr, cm−1): 3434.8, 2528.2, 1645.6, 1434.7.
rac-4a-hydroperoxy-1,2,3,4,4a,5,6,7-octahydronaphthalene (8a):
1H NMR (400 MHz, CDCl3, ppm): ı = 7.60 (bs, 1 H), 5.68 (dd, 1
H, J = 4.8, 2.6 Hz), 2.31–1.20 (m, 14 H). 13C NMR (100 MHz, CDCl3
CDCl3, ppm) ı = 136.3, 127.4, 81.4, 35.3, 32.5, 32.3, 27.5, 25.8, 21.6,
18.9. IR (KBr, cm−1): 3109.2, 2868.3, 1560.8, 1384.6, 1245.7, 903.5.
rac-decahydronaphthalene-1,4a,8a-triol (8b): 1H NMR (400 MHz,
CDCl3, ppm): ı = 3.92 (dd, 1 H, J = 10.0, 4.8 Hz), 2.12–1.06 (m, 14 H).
13C NMR (100 MHz, CDCl3, ppm) ı = 78.4, 75.1, 70.9, 42.5, 30.1, 27.5,
27.0, 26.1, 20.0, 18.1. IR (KBr, cm−1): 3550.2, 2929.9, 1568.4, 1169.2.
rac-2-hydroperoxy-1,2-dihydronaphthalene (9a): 1H NMR
(400 MHz, CDCl3, ppm): ı = 7.26–7.08 (m, 4 H), 6.73 (d, 1 H,
J = 9.6 Hz), 6.04 (dd, 1 H, J = 9.6, 4.8 Hz), 4.81 (m, 1 H), 3.35 (dd, 1 H,
J = 17.2, 4.8 Hz), 3.03 (dd, 1 H, J = 17.2, 6.05 Hz). 13C NMR (100 MHz,
CDCl3, ppm): 133.7, 133.1, 132.4, 128.6, 128.3, 127.3, 127.0, 123.2,
77.3, 31.8. IR (KBr, cm−1): 3390.8, 3042.0, 1634.3, 1488.1, 1451.7,
997.4, 786.1.
rac-1,2,3,4-tetrahydronaphthalene-1,2/3-triol (9b): 1H NMR
(400 MHz, D2O, ppm): ı = 7.33–7.18 (m, 4 H), 4.63 (m, 1 H), 4.01
(m, 1 H), 3.59 (m, 1 H)), 3.05–2.52 (m, 2 H). 13C NMR (100 MHz,
D2O, ppm): 138.5, 137.3, 130.3, 129.7, 128.9, 128.5, 76.5, 72.8,
68.9, 38.9. IR (KBr, cm−1): 3502.4, 3008.4, 1733.6, 1370.0, 1229.5,
1016.4.
On the other hand, the bicyclic allylic hydroper-
oxides were also studied under the same reaction
rac-3-hydroperoxy-7-oxabicyclo[4.1.0]hept-4-ene (10a): 1H NMR
(400 MHz, CDCl3, ppm): ı = 8.09 (bs, 1 H), 6.13 (ddd, 1 H, J = 10.2,
5.2, 1.8 Hz), 6.03 (dd, 1 H, J = 10.2, 1.9 Hz), 4.58 (m, 1 H), 3.53 (m,
1 H), 3.31 (m, 1 H), 2.58 (ddd, 1 H, J = 14.1, 7.8, 2.4 Hz), 1.43 (ddd,
1 H, J = 14.1, 10.2, 1.1 Hz). 13C NMR (100 MHz, CDCl3, ppm): 135.5,
126.5, 78.6, 53.6, 49.1, 27.3. IR (KBr, cm−1): 3366.6, 2934.3, 1650.7,
1600.8, 1430.9, 1392.5, 944.8.
conditions.
rac-2-hydroperoxy-1,2-dihydronaphthalane (9a) gave the
In
the
presence
of
rac-4a-
expected products of rac-decahydro naphthalene-1,4a,8a-triol (8b)
(88%) and rac-2,3-dihydroxy-1,2,3,4-tetrahydronaphthalen-1,2/3-
4-ene (10a) was converted to rac-cyclohex-5-ene-1,2,4-triol (10b)
and rac-7-oxabicyclo[4.1.0]heptane-2,3,4-triol (10c) with the yield
of 92% and 8%, respectively in the presence of zeolite-Os0 catalyst
(Scheme 5).
rac-cyclohex-5-ene-1,2,4-triol (10b): 1H NMR (400 MHz, D2O,
ppm): ı = 5.75 (d, 1 H, J = 10.5 Hz), 5.66 (dd, 1 H, J = 10.5, 1.8 Hz),
4.28 (q, 1 H, J = 3.8 Hz), 3.91 (ddd, 1 H, J = 7.2, 1.7, 1.4 Hz), 3.73 (ddd,
J = 1 H 11.9, 7.2, 4.7 Hz), 1.82 (m, 2 H). 13C NMR (100 MHz, D2O,
ppm): 133.8, 132.3, 74.3, 71.4, 67.1, 38.7. IR (KBr, cm−1): 3387.2,