Practical iron-catalyzed hydrogen peroxide epoxidation of aromatic olefins using a combination of two kinds of simple picolinate ligands under halide-free reaction conditions

Article abstract of DOI:10.1002/adsc.201300774

High-yield syntheses of epoxides using an iron complex having two types of picolinates in the presence of hydrogen peroxide under halide-free reaction conditions were achieved. The reaction is very simple. The complex, prepared with iron(II) acetate, 2-pi

Full text of DOI:10.1002/adsc.201300774

Supporting Information
©
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013

Supporting Information
Practical Iron–Catalyzed Hydrogen Peroxide Epoxidation of Aromatic
Olefins Using a Combination of Two Kinds of Simple Picolinate
Ligands under Halide–Free Reaction Conditions
Takefumi Chishiro, Yoshihiro Kon,* Takuya Nakashima, Midori Goto, and Kazuhiko Sato*
Contents
1
2
3
4
5
6
7
8
9
1
.
Instrumentation and Chemicals
S2
S3
.
Experimental procedures for Epoxidation of styrene derivatives
NMR spectroscopy / Evans method
.
S5
.
Epoxidation using Fe(pic)(Me-pic)
2
catalyst (1)
S6
.
Hammett plots for epoxidation of p-styrene derivatives
Epoxidation of styrene using various iron metal precursors
ESI-MS spectra of 1 in MeCN solution
S8
.
S9
.
S10
S12
S13
S17
S19
S20
.
Plausible Reaction Mechanism
.
Single-crystal X–ray analyses of 1 and (Me-pic)
Characterization Data for Compounds
References
2 2
FeOFe(Me-pic)
0.
11.
1
13
1
2.
H and C NMR Spectra
-S1-

1. Instrumentation and Chemicals
1
13
H NMR (400 MHz) and C NMR (100 MHz) spectra were recorded on JEOL 400 MHz NMR
spectrometers. All spectra were recorded at 25 ± 1 ºC. Chemical shifts (δ) are in parts per million
1
at 77.0 ppm for 13
relative to tetramethylsilane at 0.00 ppm for H and relative to residual CHCl
3
C
unless otherwise noted. Gas chromatographic (GC) analyses were performed on a Shimadzu
GC-2014 using an INERT CAP column (0.25 mm x 30 m, GL Sciences Inc.). All samples were
analyzed and quantified by using biphenyl as an internal standard. Electron spray mass spectra were
measured on a Waters micromass ZQ mass spectrometer. Characteristic fragments with their relative
intensities in percentages are shown. Melting points were measured with a Mettler FP90 microscope
on an object slide. Elemental analyses were measured on Thermo Fisher Scientific Inc. Flash2000.
In X-ray crystallographic analyses, data were collected on a Bruker APEX-II CCD diffractometer
using graphite-monochromated MoKradiation. The structures were solved by direct methods
2
(
SHELXS-97) and refined by full matrix least-squares techniques on F (SHELXL-97).
2
-Picolinic acid (picH), 6-methyl-2-picolinic acid (Me-picH), styrene, 4-methylstyrene,
-methylstyrene, cis--methylstyrene, trans--methylstyrene, styrene oxide, trans-stilbene,
trans-stilbene oxide, 1-octene, cyclooctene, epoxycyclooctane, 4-methoxystyrene, 4-nitrostyrene,
,2-epoxycyclohexane, α-Pinene, α-Pinene oxide and biphenyl were purchased from Tokyo Kasei
Inc., iron(II) acetate, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-(trifluoromethyl)styrene,
-phenylstyrene, N-tert-butyl--phenylnitrone, and 4-chlorostyrene oxide were from
Shigma-Aldrich, iron(III) nitrate nonahydrate, iron(III) chloride, 1,2-epoxyoctane, duroquinone,
N,N’-dimethylacetamide, cyclohexene, toluene, THF, pyridine, tBuOH, Et N, CDCl , and MeCN
1
4
3
3
were from Wako Pure Chemical Industries, Ltd., 35% hydrogen peroxide aqueous solution was from
Kanto Chemical Co., Inc., and iron(III) acetate hydroxide was form Kishida Inc., respectively. All
chemicals were used as received.
4-Bromostyrene oxide, 4-fluorostyrene oxide,
4
-(trifluoromethyl)styrene oxide, 4-methylstyrene oxide, 4-phenylstyrene oxide, -methylstyrene
oxide, cis--methylstyrene oxide, and trans--methylstyrene oxide were prepared according to
literature.[1] Oxidation reactions of styrenes in small scale were performed using ChemiStation
(
Tokyo Rika Inc.) equipped with thermostated apparatus.
-S2-

2
. Experimental procedures for Epoxidation of styrene derivatives
Preparation of catalyst solution.
Iron(II) acetate (43.5 mg, 0.25 mmol), picH (30.8 mg, 0.25 mmol), and Me-picH (34.3 mg, 0.25
mmol) were suspended in CH
until almost all of iron acetate was dissolved (ca. 15 min), then the solution was filtered with
membrane filter (pour size: 0.20 m). The filtrate was diluted with CH CN, to adjust the total
3
CN (20 mL). The mixture was warmed to 40 ºC with gentle stirring
3
-
1
volume to 25 mL (the concentration of iron: 0.01 mol·L ). The catalyst solutions with the different
ligand ratio were also prepared in the same manner using the appropriate amount of picH and
Me-picH. This procedure was also applied for preparation of catalyst solution with other iron salts
such as iron(III) nitrate.
Typical procedure for the epoxidation reaction.
Olefin (1.0 mmol) was dissolved in 2 mL of the catalyst solution. 35% aqueous H
.25 mmol) was added dropwise to the solution via a syringe pump for 10 min at 25 ºC, and the
reaction solution was further stirred for 5 min at 25 ºC. To the resulting mixutre was then added
0mL of CH CN and measured amount of biphenyl (as an internal standard for GC analysis). The
2 2
O (112.8 L,
1
1
3
conversion of substrate and the yield of styrene oxide were determined by GC analysis. Products
were identified by comparison to the GC retention time of authentic samples. The same reaction
was performed three times for each substrate, confirming the errors of less than 5% in conversion
and yield for each runs.
Epoxidation of styrene (100-g scale).
Styrene (100 g, 0.96 mol) was dissolved in 1.92 L of the catalyst solution prepared above. To
2 2
the solution was added 35% aqueous H O (106 mL, 1.2 mol) dropwise via a dropping funnel for 30
min at 25 ºC, and the reaction solution was further stirred for 5 min at 25 ºC. Saturated sodium
thiosulfate solution (25 mL) was added to the resulting solution, and the mixture was stirred for
3
another 5 min at 25 ºC. The organic layer was separated, and CH CN was removed by rotary
evaporator. The residual crude product was purified by distillation under reduced pressure (62 – 65
1
ºC at 4.0 mmHg), to give 92.7 g of styrene oxide (80% yield). The structure was characterized by H
13
1
and CNMR analyses. H NMR (400 MHz, CDCl
3
.5, 4.0 Hz, 1H), 3.83 (dd, J = 4.0, 2.5 Hz, 1H), 7.21 – 7.35 (m, 5H); C NMR (100 MHz, CDCl ): δ
3
): δ = 2.77 (dd, J = 5.5, 2.5 Hz, 1H), 3.11 (dd, J =
1
3
5
=
51.1, 52.2, 125.4, 128.1, 128.4, 137.5.
III
2
Synthesis of Fe (pic)(Me-pic) .
II
Fe (OAc)
2
(174 mg, 1.00 mmol), picH (123.2 mg, 1.00 mmol) and Me–picH (274.4 mg, 2.00 mmol)
-S3-

were suspended in MeCN (80 mL). The mixture was warmed to 40 ºC with gentle stirring until
almost all of the iron acetate was dissolved (ca. 15 min). The solution was then filtered.
III
Recrystallization from MeCN afforded pure Fe (pic)(Me-pic)
2
1 (207.8 mg, 0.462 mmol, 46%
yield) as pale yellow crystals. M.p. 227 ºC (decomp.); MS (ESI+) m/z (%): 465 (7) [Fe (Me-pic)
3
+
+
+
+
+
H] , 451 (16) [Fe(pic)(Me-pic)
2
+ H] , 437 (5) [Fe(pic)
2
(Me-pic) + H] , 138 (100) [Me-picH + H] ;
Anal. Calcd for C20 : C 53.36; H 3.58; N 9.33. Found: C 53.35; H 3.42; N 9.29.
3 6
H16FeN O
-S4-

3
.
NMR spectroscopy / Evans method
3
In a typical experiment, catalyst solution prepared in CD CN (concentration of iron: 10mM) was
3
placed in the sample tube. The coaxial insert as internal reference was filled with CD CN, placed
1
inside the sample tube and then sealed with the suitable cap. H NMR was obtained and referenced
as usual, with the paramagnetically–shifted solvent peak occuring downfield of the reference solvent
peak.
The equation eff / 
B
= 2.828 (
M
T)1/2 was used for the calculation of the magnetic moment,
M
where T is the temperature of the measurement (298 K) and  is determined by the following
equation (Eq. S1).[2]
where,
p
3
-1

=
Molar paramagnetic susceptibility (cm mol )
f = Frequency difference between the two peaks of the inner and outer tube (Hz)
f = Frequency of the NMR instrument (Hz)
m = Mass of the substance in 1 cm3 of solution (g cm )
M

-3
3
-1
0
= Mass susceptibility of the solvent (cm mol )
-3
d = Density of the solvent (g cm )
0
-3
d = Density of the solution (g cm )
s
P
-1
M = Molecular weight of the substance (g mol )
dia
M

3
-1
= Diamagnetic correction to the magnetic susceptibility (cm mol )
The densities of the solutions were found almost equal to that of solvent because of the relatively
low concentration, and so the (d -ds)/m term was neglected. Diamagnetic corrections were calculated
form Pascal’s constants to be found insignificant, and were not applied. MP values of
Fe(pic)(Me-pic) ] = 450.21, based on the expected formulae from ESI-MS observation, was
0
[
2
tentatively used for the calculation. The effective magnetic moments were determined by average
III
of three independent runs, to be eff = 5.1 
B
. This result indicate that the iron ion is high-spin Fe in
the catalyst solutions.
-S5-

4
. Epoxidation using Fe(pic)(Me-pic)
Styrene (114.6 L, 1.0 mmol), 1 (9.0 mg, 0.02 mmol), and MeCN (2 mL) were added into test
tube. 35% aqueous H (112.8 L, 1.25 mmol) was added to the solution dropwise via a syringe
pump for 10 min at 25 ºC, and the reaction solution was further stirred for 5 min at 25 ºC. To the
resulting mixutre was then added 10mL of CH CN and measured amount of biphenyl (as an internal
2
catalyst (1)
2
O
2
3
standard for GC analysis). The conversion of substrate and the yield of styrene oxide were
determined by GC analysis. The addition of 0.02 eq. of picH to the same reaction diminished the
yield of styrene oxide (15% yield).
2 2
Table S1. Epoxidation of styrene with 35% H O
using 1 in the presence of various solvents[a]
Conv. [%][b] Yield [%][b]
Sel. [%][c]
Entry
Solvent [mL]
none
1
2
3
4
5
6
0
0
93
0
0
95
0
MeCN [2]
Toluene [2]
THF [2]
98
0
19
81
33
13
59
3
68
73
9
tBuOH [2]
Pyridine [2]
[
2 2
a] Reaction was run using styrene (1.0 mmol), 35% H O , and 1 in a 100:125: 2 molar ratio at 25 ˚C for 15 min in
the presence of various solvent (2 mL). [b] Determined by GC analysis. [c] 100 x yield / conversion.
2 2
Table S2. Epoxidation of styrene with 35% H O
using Iron catalysts [a]
Conv. [%][b] Yield [%][b]
Sel. [%][c]
Entry
Iron catalyst (with additive) [eq.]
1
2
3
1 [0.02]
98
18
78
93
15
66
95
83
85
1 [0.02] + picH [0.02]
1 [0.02] + Me-picH [0.02]
[
2 2
a] Reaction was run using styrene (1.0 mmol), 35% H O , and iron catalyst (with additive) in a 100:125: 2 molar
ratio at 25 ˚C for 15 min in MeCN (2 mL) solution. [b] Determined by GC analysis. [c] 100 x yield / conversion.
-S6-

2 2
Table S3. Epoxidation of styrene with 35% H O using 1 in the presence of various radical trapping
agents[a]
Conv. [%][b] Yield [%][b]
Sel. [%][c]
Entry
Radical trapping agent [eq.]
1
2
3
4
5
none
98
93
90
21
88
83
95
93
62
93
90
BPN [0.02] [d]
BPN [1]
97
34
Duroquinone[0.02]
Duroquinone[1]
95
92
[
a] Reaction was run using styrene (1.0 mmol), 35% H
2
O
2
2
, and Fe(Pic)(Me-Pic) in a 100:125: 2 molar ratio at 25 ˚C
for 15 min in the presence of various radical trapping agents. [b] Determined by GC analysis. [c] 100 x yield /
conversion. [d] BPN = N-tert-Butyl-α-phenylnitrone.
-S7-

5
. Hammett plots for epoxidation of p-styrene derivatives
A test tube equipped with a magnetic stirring bar and a reflux condenser was charged with 1.0
mmol of p-substituted styrene, 1.0 mmol of styrene, and 4.5 mg (0.01 mmol) of 1. After the mixture
was vigorously stirred at 25 ˚C for 1 min, 0.02 ml (0.20 mmol) of aqueous 35% H was added
2
O
2
dropwise over the course of 3 min, and 1 was then separated by filtration. The disappearance of the
substrates was monitored by GC analysis with 0.2 mmol of internal standard, typically biphenyl.
Initial relative rates (log(k
X H
/k )) thus determined were 1.06 (p-OMe), 0.50 (p-Me), 0.00 (p-H), -0.14
(
p-Cl), and -0.64 (p-NO ), respectively.
2
Table S4. Competitive oxidation of p-substituted styrenes[a]
Entry p-substituents(X)
Conv. of p-X[%] [b]
Conv. of p-H [%][b]
1
2
3
4
Me
Cl
7.7
2.5
2.5
3.5
1.0
7.2
OMe
11.4
1.6
NO
2
[
a] Reaction was run using a 1:1 mixture of styrene and p-substituted styrenes (2.0 mmol), 35% H
2 2
O , and 1 in a
1
00:10:0.5 molar ratio at 25 ˚C for 3 min. [b] Determined by GC analysis.
1
.5
1
y = -1.11x + 0.11
y = -1.1064x + 0.1139
2
R =
R
0
² =.9
0.9681
7
0
.5
0
-
1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
-0.5
-1
σ+
Figure S1. Hammett Plot
-S8-

6
. Epoxidation of styrene using various iron metal precursors
Preparation of catalyst solution with other iron metal salts and epoxidation reaction of styrene
were performed according to procedures described above. The results were summarized in Table S5.
Iron(III) acetate-hydroxide showed similar reactivity with that prepared from iron(II) acetate (Entries
1
and 2). Iron(III) nitrate could also be used (Entry 3), however, 0.06 equiv of base, such as
triethylamine, was required for the reaction (Entry 4). In this case, larger amount of base also
inhibited the reaction (Entry 5). On the other hand, iron(III) chloride was ineffective (Entries 6 and
7
), presumably because of inactivation of the catalyst by the coordination of chloride toward iron ion,
or catalytic degradation of H
2
O
2
by chloride anion.[3]
2 2
Table S5. Epoxidation of styrene with 35% H O
using various iron metal precursors[a]
Entry
Iron precursor
Conversion, %[b]
Yield, %[b]
II
1
2
3
4
5
6
7
Fe (OAc)
2
99
99
99
0
95
84
83
0
III
Fe (OAc)
2
(OH)
O + 0.06 equiv Et
·9H
III
Fe (NO
3
)
3
·9H
2
3
N
N
III
Fe (NO
3
)
3
2
O
III
Fe (NO
3
)
3
·9H
2
O + 0.08 equiv Et
3
0
0
III
Fe Cl
3
25
0
18
0
III
3 3
Fe Cl + 0.06 equiv Et N
[
a] Reaction conditions: H
2
O
2
: styrene : Fe : picH : Me-picH = 140 : 100 : 2 : 2 : 2 molar ratio in CH
3
CN with
substrate concentration of 500 mM, 25 ºC, dropwise addition of H
Determined by GC using biphenyl as an internal standard. Average of three runs.
2 2
O for 10 min and further stirring for 5 min. [b]
-S9-

7
. ESI-MS spectra of 1
ESI-MS measurements were preformed with a Waters micromass ZQ mass spectrometer in the
positive ion mode. Direct introduction of a sample (complex 1 in MeCN) into the mass spectrometer
was carried out by using syringe-pump. Data were collected at a capillary voltage of 3500 V, a
sample cone voltage of 30 V, a desolvation temperature of 150 ºC, and a source temperature of 80 ºC.
Each data was identified by using isotopic pattern.
Figure S2. ESI-MS spectrum
-
S10-

Figure S3. Estimated structures from ESI data
-S11-

8
. Plausible Reaction Mechanism
At the reaction mechanism, we have no rationale or experimental data for iron(III)
active species and many great previous reports suggested that an iron(V) oxo species
effectively work for epoxidation supported by spectroscopic and theoretical studies as
III
mentioned by reviewer. We revised active species from Fe (pic)(Me-pic)OOH to
V
Fe (O)(pic)(Me–pic)(OOCC
5
H N-Me) as an iron(V) oxo active species derived from
3
III
dehydration of Fe (pic)(Me-pic) (Me-picH) OOH as shown below.
Figure S4. Plausible Mechanism
In this mechanism, an iron atom at iron(V) oxo species do not receive efficient electron
donation from picolinate ligands different from the case of previously reported iron
complexes coordinated by donar N-ligands, therefore it is reasonable that the system
shown in this paper did not show high reactivities for less reactive terminal olefins.
However it showed moderate reactivities with high selectivities for styrene epoxidation
by the optimization of ligands in iron complex.
-
S12-

9
9
. Single-crystal X–ray analyses of 1 and (Me-pic)
2
FeOFe(Me-pic)
2
-1. X–ray analysis of 1
Table S6. Crystal data and structure refinement
Empirical formula
Formula weight
C
20
H
16 Fe N
3
O
6
450.21
Temperature
183(2) K
0.71073 Å
Monoclinic
C 2/c
Wavelength
Crystal system
Space group
Unit cell dimensions
a = 29.653(12) Å
b = 8.330(4) Å
c = 15.191(6) Å
= 90°
= 90.896(4)°
 = 90°
3
Volume
3752(3) Å
Z
8
3
Density (calculated)
Absorption coefficient
F(000)
1.594 g/m
-1
0.849 mm
1848
3
Crystal size
0.20 x 0.08 x 0.05 mm
1.37 to 25.58°
Theta range for data collection
Index ranges
-35<=h<=35, -10<=k<=10, -18<=l<=18
16293
Reflections collected
Independent reflections
Completeness to theta = 25.58°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
3490 [R(int) = 0.0302]
99.1 %
Semi-empirical from equivalents
0.9586 and 0.8480
2
Full-matrix least-squares on F
3490 / 0 / 273
2
Goodness-of-fit on F
1.060
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0409, wR2 = 0.1103
R1 = 0.0499, wR2 = 0.1158
-3
0.925 and -0.370 eÅ
Largest diff. peak and hole
-
S13-

Figure S5. ORTEP drawings of 1 with atom labeling scheme. Hydrogen atoms are omitted for
clarity.
Figure S6. Views of Crystal Packing of 1.
(a)
b)
c)
Figure S7. Views of Crystal Packing of 1. (a) along the a axis. (b) along the b axis. (c) along the c
axis.
-
S14-

9
2 2
-2. X–ray analysis of (Me-pic) FeOFe(Me-pic) (including one MeCN)
Table S10. Crystal data and structure refinement for (Me-pic)
2
2
FeOFe(Me-pic) (MeCN).
Empirical formula
Formula weight
Temperature
30 2 5 9
C H27 Fe N O
713.27
183(2) K
Wavelength
0.71073 Å
Tetragonal
P 4/ncc
Crystal system
Space group
Unit cell dimensions
a = 14.3498(11) Å
b = 14.3498(11) Å
c = 15.6138(16) Å
= 90°
= 90°
 = 90°
3
Volume
3215.1(5) Å
Z
4
3
Density (calculated)
Absorption coefficient
F(000)
1.474 Mg/m
-1
0.962 mm
1464
3
Crystal size
0.25 x 0.20 x 0.07 mm
2.01 to 28.61°
Theta range for data collection
Index ranges
-19<=h<=16, -19<=k<=19, -19<=l<=20
19650
Reflections collected
Independent reflections
Completeness to theta = 27.0°
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
1979 [R(int) = 0.0225]
99.9 %
Semi-empirical from equivalents
0.9497 and 0.8357
2
Full-matrix least-squares on F
1979 / 2 / 110
2
Goodness-of-fit on F
1.045
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0304, wR2 = 0.0929
R1 = 0.0401, wR2 = 0.1014
-3
0.642 and -0.473 eÅ
Largest diff. peak and hole
-
S15-

2 2
Figure S8. ORTEP drawings of (Me-pic) FeOFe(Me-pic) (MeCN) with atom labeling scheme.
Hydrogen atoms are omitted for clarity.
Figure S9. Views of Crystal Packing of (Me-pic)
2
FeOFe(Me-pic)
2
(MeCN).
c)
(a)
b)
2 2
Figure S10. Views of Crystal Packing of (Me-pic) FeOFe(Me-pic) (MeCN). (a) along the a axis. (b)
along the b axis. (c) along the c axis.
-
S16-

1
0. Characterization Data for Compounds
styrene oxide[4]
1H NMR (400 MHz, CDCl
3
): δ = 2.77 (dd, J = 5.5, 2.5 Hz, 1H), 3.11 (dd, J = 5.5, 4.0 Hz, 1H), 3.83
13
(
3
dd, J = 4.0, 2.5 Hz, 1H), 7.21 – 7.35 (m, 5H); C NMR (100 MHz, CDCl ): δ = 51.1, 52.2, 125.4,
1
28.1, 128.4, 137.5.
4
-fluorostyrene oxide[5]
1H NMR (400 MHz, CDCl
3
): δ = 2.75 (dd, J = 5.6, 2.6 Hz, 1H), 3.12 (dd, J = 5.6, 4.0 Hz, 1H), 3.84
1
3
(
dd, J = 4.0, 2.6 Hz, 1H), 6.95 - 7.10 (m, 2 H), 7.16 - 7.32 (m, 2H); C NMR (100 MHz, CDCl
51.1, 51.8, 115.4 (d, J = 20 Hz), 127.1 (d, J = 7 Hz), 133.3 (d, J = 2 Hz), 162.6 (d, J = 24 Hz).
-chlorostyrene oxide[4]
1H NMR (400 MHz, CDCl
3
): δ
=
4
3
): δ = 2.74 (dd, J = 5.5, 2.5 Hz, 1H), 3.13 (dd, J = 5.5, 4.0 Hz, 1H), 3.82
dd, J = 4.0, 2.5 Hz, 1H), 7.20 (d, J = 8.5 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H); 13C NMR (100 MHz,
(
3
CDCl ): δ = 51.2, 51.7, 126.8, 128.6, 133.8, 136.1.
4
-bromostyrene oxide[6]
1H NMR (400 MHz, CDCl
3
): δ = 2.74 (dd, J = 5.5, 2.5 Hz, 1H), 3.13 (dd, J = 5.5, 4.1 Hz, 1H), 3.81
1
3
(
3
dd, J = 4.1, 2.5 Hz, 1H), 7.08-7.20 (m, 2H), 7.40-7.52 (m, 2H); C NMR (100 MHz, CDCl ): δ =
5
1.2, 51.8, 121.9, 127.1, 131.6, 136.7.
4
-(trifluoromethyl)styrene oxide [7]
1H NMR (400 MHz, CDCl
3
): δ = 2.77 (dd, J = 5.6, 2.6 Hz, 1H), 3.18 (dd, J = 5.6, 4.0 Hz, 1H), 3.91
(
dd, J = 4.0, 2.6 Hz, 1H), 7.39 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 8.1 Hz, 2H); 13C NMR (100 MHz,
3
CDCl ): δ = 51.4, 51.7, 125.4 (q, J = 3.8 Hz), 125.7, 141.8.
4
-Methylstyrene oxide[5]
1H NMR (400 MHz, CDCl
Hz, 1H), 3.82 (dd, J = 4.1, 2.6 Hz, 1H), 7.10-7.20 (m, 4H); C NMR (100 MHz, CDCl
3
): δ = 2.33 (s, 3H), 2.78 (dd, J = 5.5, 2.6 Hz, 1H), 3.11 (dd, J = 5.5, 4.1
1
3
3
): δ = 21.1,
5
1.0, 52.3, 125.4, 129.1, 134.5, 137.9.
4
-phenylstyrene oxide [9]
1H NMR (400 MHz, CDCl
3
): δ = 2.83 (dd, J = 2.7, 5.5 Hz, 1H), 3.16 (dd, J = 4.1, 5.5 Hz, 1H), 3.89
13
(
dd, J = 2.7, 4.1 Hz, 1H), 7.27-7.37 (m, 3H), 7.39-7.46 (m, 2H), 7.51-7.62 (m, 4H); C NMR (100
3
MHz, CDCl ): δ = 51.2, 52.2, 125.9, 127.0, 127.2, 127.3, 128.7, 136.6, 140.6, 141.1.
α-methylstyrene oxide[10]
1H NMR (400 MHz, CDCl
): δ = 1.71 (s, 3H), 2.79 (d, J = 5.4 Hz, 1H), 2.96 (d, J = 5.4 Hz, 1H),
): δ = 21.8, 56.7, 57.0, 125.2, 127.4, 128.3, 141.1.
3
1
3
7
.21 – 7.42 (m, 5H); C NMR (100 MHz, CDCl
trans-β-methylstyrene oxide[11]
1H NMR (400 MHz, CDCl
): δ = 1.44 (d, J = 6.8 Hz, 3H), 3.03 (dq, J = 6.8, 2.6 Hz, 1H), 3.56 (d, J
2.6 Hz, 1H), 7.22 – 7.36 (m, 5H); C NMR (100 MHz, CDCl
28.4, 137.7.
3
3
13
=
3
): δ = 17.9, 59.0, 59.5, 125.5, 127.9,
1
-
S17-

cis-β-methylstyrene oxide[11]
1H NMR (400 MHz, CDCl
): δ = 1.08 (d, J = 7.1 Hz, 3H), 3.33 (dq, J = 7.1, 5.8 Hz, 1H), 4.05 (d, J
5.8 Hz, 1H), 7.23 – 7.40 (m, 5H); C NMR (100 MHz, CDCl
27.9, 135.5.
3
13
=
3
): δ = 12.5, 55.1, 57.5, 126.5, 127.4,
1
trans-stilbene oxide[10]
1H NMR (400 MHz, CDCl
): δ = 3.86 (s, 2H), 7.25-7.46 (m, 10H); C NMR (100 MHz, CDCl
13
): δ
3
3
=
62.8, 125.5, 128.3, 128.5, 137.1.
,2-epoxyoctane[11]
1H NMR (400 MHz, CDCl
Hz, 1H), 2.74 (dd, J = 3.9, 5.0 Hz, 1H), 2.88 – 2.93 (m, 1H); C NMR (100 MHz, CDCl
1
3
): δ = 0.89 (t, J = 7.0 Hz, 3H), 1.20 - 1.64 (m, 10H), 2.46 (dd, J = 2.7, 5.0
1
3
3
): δ = 14.0,
2
2.5, 25.9, 29.1, 31.7, 32.5, 47.0, 52.3.
1
,2-epoxycyclooctane[8]
1H NMR (400 MHz, CDCl
3
): δ = 1.16 - 1.36 (m, 2H), 1.36 - 1.72 (m, 8H) , 2.05 - 2.25 (m, 2H) ,
1
3
2
3
.82 – 3.00 (m, 2H); C NMR (100 MHz, CDCl ): δ = 25.6, 26.3, 26.5, 55.6.
1
,2-epoxycyclohexane[11]
1H NMR (400 MHz, CDCl
100 MHz, CDCl ): δ = 19.4, 24.4, 52.1.
α-Pinene oxide[12]
1H NMR (400 MHz, CDCl
): δ = 1.15-1.49 (m, 4H), 1.74-2.01 (m, 4H) , 3.12 (s, 2H); 13C NMR
3
(
3
3
): δ = 0.94 (s, 3H), 1.29 (s, 3H), 1.34 (s, 3H), 1.62 (d, J = 9.6 Hz, 1H),
.70-1.75 (br m, 1H), 1.87-2.03 (m, 4H), 3.07 (dd, J = 4.1, 1.4 Hz, 1H); 13C NMR (100 MHz,
1
3
CDCl ): δ = 20.2, 22.4, 25.9, 26.7, 27.6, 39.7, 40.5, 45.1, 56.9, 60.3.
-
S18-

11. References:
[
[
1]
2]
M. Imuta, H. Ziffer, J. Org. Chem. 1979, 44, 1351.
a) W. D. Phillips, M. Poe, Meth. Enzymol. 1972, 24, 304; b) E. M. Schubert, J. Chem.
Educ. 1992, 26, 62.
[
3]
D.D. Davis, D.R. Kemp in Kirk–Othmer Encyclopedia of Chemical Technology, 4th ed.,
vol. 1, (Eds.: J.I. Kroscwitz, M. Howe-Grant), John Wiley & Sons, Inc., New York, 1991,
pp. 466.
[
[
4]
5]
A. Piccinini, S.A. Kavanagh, P.B. Connon, S.J. Connon, Org. Lett. 2010, 12, 608.
M.K. Tse, M. Klawonn, S. Bhor, C. Döbler, G. Anilkumar, H. Hugl, W. Mägerlein, M.
Beller, Org. Lett. 2005, 7, 987.
[
[
[
6]
7]
8]
S. Pedragosa-Moreau, C. Morisseau, J. Zylber, A. Archelas, J. Baratti, R. Furstoss, J. Org.
Chem. 1996, 61, 7402.
F.G. Gelalcha, G. Anilkumar, M.K. Tse, A. Brueckner, M. Beller, Chem. Eur. J. 2008, 14,
7
687.
K. Sato, M. Aoki, M. Ogawa, T. Hashimoto, D. Panyella, R. Noyori, Bull. Chem. Soc. Jpn.
997, 70, 905.
1
[
[
9]
K. Matsumoto, T. Kubo, T. Katsuki, Chem. Eur. J. 2009, 15, 6573.
M.W.C. Robinson, A.M. Davies, R. Buckle, I. Mabbett, S.H. Taylor, A.E. Graham, Org.
Biomol. Chem. 2009, 7, 2559.
10]
[
11]
12]
B. Kang, M. Kim, J. Lee, Y. Do, S. Chang, J. Org. Chem. 2006, 71, 6721.
H. Hachiya, Y. Kon, Y. Ono, K. Takumi, N. Sasagawa, Y. Ezaki, K. Sato, Synthesis 2012,
[
4
4, 1672.
-
S19-

1
13
1
2. H and C NMR Spectra:
1
Styrene Oxide H NMR (400MHz, CDCl
3
)
O
7
7
7
7
7
7
.33
.31
.30
.28
.27
.25
4
.75
3
3
3
3
3
3
3
3
.84
.83
.82
.12
.12
.11
.10
.10
0
.94
1
.00
.99
0
2.78
2
2
2
.77
.77
.76
0
.00
-
S20-

13
3
Styrene Oxide C NMR (100MHz, CDCl )
1
37.50
1
1
1
28.37
28.05
25.37
77.31
77.00
76.68
5
5
2.24
1.09
-
S21-

1
4
3
-Fluorostyrene Oxide H NMR (400MHz, CDCl )
7
7
7
7
7
7
7
7
7
7
6
.28
.26
.24
.23
.22
.20
.07
.05
.02
.00
.98
1
1
.89
.88
3
3
3
3
3
3
3
2
2
2
2
.84
.84
.83
.13
.12
.12
.11
.76
.76
.75
.74
0
.93
1
.00
.00
1
0
.00
-
S22-

13
4
3
-Fluorostyrene Oxide C NMR (100MHz, CDCl )
1
1
63.83
61.38
1
1
1
1
33.27
33.24
27.14
27.06
1
1
15.51
15.29
77.32
77.00
76.69
5
5
1.77
1.09
-
S23-

1
4
3
-Chlorostyrene Oxide H NMR (400MHz, CDCl )
7
.32
1
.99
.05
7.30
7
7
2
.21
.19
3
3
3
3
3
3
2
2
2
2
.83
.82
.81
.14
.13
.12
.75
.74
.74
.73
1
.00
1
.07
.07
1
0
.00
-
S24-

13
4
3
-Chlorostyrene Oxide C NMR (100MHz, CDCl )
O
Cl
1
1
1
1
36.12
33.83
28.62
26.76
77.31
77.00
76.68
5
5
1.71
1.17
-
S25-

1
4
3
-Bromostyrene Oxide H NMR (400MHz, CDCl )
O
Br
7
7
7
7
7
7
7
7
.49
.47
.45
.43
.18
.15
.13
.11
1
.95
1
.91
3
3
3
3
3
3
2
2
2
2
.82
.81
.80
.14
.13
.12
.75
.74
.73
.73
0
.93
0
.99
.00
1
0
.00
-
S26-

13
4
3
-Bromostyrene Oxide C NMR (100MHz, CDCl )
O
Br
1
1
1
1
36.65
31.56
27.08
21.93
77.31
77.00
76.69
5
5
1.76
1.15
-
S27-

1
4
3
-(Trifluoromethyl)styrene oxide H NMR (400MHz, CDCl )
7
7
.61
.60
1
1
.95
.95
7.59
7.40
7
7
7
.39
.38
.26
0
.97
3
.91
3
3
3
2
2
2
2
.20
.18
.17
.78
.77
.76
.76
1
.02
1
.00
0
.00
-
S28-

1
3
4
3
-(Trifluoromethyl)styrene oxide C NMR (100MHz, CDCl )
1
41.80
1
1
1
25.71
25.46
25.43
77.31
77.00
76.69
5
5
1.70
1.41
-
S29-