Epoxide Formation by Indirect Electroreductive Coupling between Aldehydes or Ketones and Activated gem-Dichloro Compounds

Article abstract of DOI:10.1055/s-2004-815915

Epoxides are prepared by indirect electroreductive coupling of carbonyl compounds (aldehydes or ketones) and activated gem-dichloro compounds. This process is more efficient with aryl ketones than with aryl aldehydes. Though yields are only moderate, this

Full text of DOI:10.1055/s-2004-815915

PAPER
389
Epoxide Formation by Indirect Electroreductive Coupling between Aldehydes
or Ketones and Activated gem-Dichloro Compounds
E
poxide Form
.
ation by Cou
O
pling between Ald
u
ehydes or
K
d
etones and D
e
ichloro Co
y
mpounds er, E. Léonel, J. P. Paugam,* J.-Y. Nédélec
LECSO-CNRS UMR 7582, Université Paris XII-Val de Marne, 2 à 8 rue H. Dunant, 94320 Thiais, France
Fax +33(01)49781148; E-mail: paugam@glvt-cnrs.fr
Received 5 November 2003; revised 28 November 2003
related reactions involving benzal bromides in the pres-
Abstract: Epoxides are prepared by indirect electroreductive cou-
pling of carbonyl compounds (aldehydes or ketones) and activated
gem-dichloro compounds. This process is more efficient with aryl
ketones than with aryl aldehydes. Though yields are only moderate,
ence of BuLi,15 or the fluorodesilylation of -bromoben-
zyltrimethylsilane with CsF in DMF.16 The thermal
degradation of 2-halogenoalkoxytributyltin compounds
this method offers the valuable advantage of avoiding the use of also has similarities with the Darzens reaction.17 The an-
strong bases or peroxides.
ions resulting from the treatment of N-tosylsulfilimines by
NaH in THF18 or by BuLi in DMSO–hexane19 are scarcely
Key words: epoxides, coupling, aldehydes, ketones, condensation,
reductions
reported in the literature. A third class of nucleophilic spe-
cies includes sulfur ylides like the Corey reagent,20,21 or
reagents derived from sulfides and aryldiazomethanes in
the presence of Rh2(OAc)422 or from -trimethylsilylben-
zylsulfonium salts by desilylation with CsF in DMF.23
Telluronium ylides can also be used.24 Lastly, we can
mention that -hydroxy sulfides, obtained from carbon-
yls, can be transformed into oxiranes by alkylation at sul-
fur followed by treatment with a base.25
We previously reported that cyclopropanes can be formed
in satisfactory yields by indirect electroreductive coupling
of electrophilic olefins (i.e. , -unsaturated esters1 or
ketones2) and activated , , -trichloro or gem-dichloro
compounds catalysed by complexes of copper and iron.
With both , -unsaturated esters and ketones, the cyclo-
condensation on the C=C bond, leading to cyclopropanes,
occurs regiospecifically, along with the formation of by-
products derived from the halo compound. With crotonal-
dehyde as the substrate, however, and in the presence of
dichlorodiphenylmethane, two cyclic products are isolat-
ed: the cyclopropane 1a in 34% yield, along with 12% of
the oxirane 1b derived from cyclocondensation on the
carbonyl2 (Scheme 1).
Our first investigation was made with benzaldehyde and
dichlorodiphenylmethane as model reagents. The reaction
conditions used are given in Scheme 1. Notably, the pre-
electrolysis involving the reduction of CuBr, along with
the oxidation of the iron anode, which generates iron ions
which can also be reduced into Fe(0), has been found nec-
essary and therefore remains unchanged throughout this
work; it is not mentioned again in the other Schemes. Un-
der these reaction conditions, we obtained a good (57%)
isolated yield of 2,2,3-triphenyloxirane (2) (Scheme 2).
This compound was, however, not quite stable under the
acidic treatment required to isolate it from the crude mix-
ture, and derived products [Ph3CCHO (3) and
Ph2CHCOPh (4)] were detected by GC–MS-analysis.
Care was taken to isolate the product by column chroma-
tography purification on neutral alumina. Tetraphenyleth-
ylene was found as the main by-product.
Ph
Ph
1a
H
10 mmol
O
Fe (anode)
Ni (cathode)
I = 0.3 A
H3C
CHO
H
3C
isolated yield: 34%
cis/trans: 45/55
Ph2CCl2
20 mmol
15 min
[Cu(0)]
[Fe(0)]
CuBr
1 mmol
Ph
Ph
DMF/pyridine
(45mL/5mL)
I = 0.1 A, 11h
-5 °C>T>-10 °C
-5 °C>T>-10 °C
1b
H3C
O
pre-electrolysis
isolated yield: 12%
Scheme 1
Ph
Ph
Ph
* Fe (anode)
Ni (cathode)
I = 0.1 A, 6 h
2
O
It was therefore very interesting to determine the scope
and limitations of this method in the formation of oxiranes
from carbonyl compounds, as there are only a few meth-
ods for such cyclocondensation reactions. Indeed, ox-
iranes are mostly prepared by epoxidation of preformed
C=C bonds.3–14 As an alternative, the formation of ox-
iranes from carbonyls requires peculiar nucleophilic re-
agents like -haloanions in the Darzens reaction, and in
+
Ph2CCl2
20 mmol
PhCHO
isolated yield: 57%
DMF/pyridine
(45mL/5mL)
-5 °C>T>-10 °C
10 mmol
3
4
Ph3CCHO
Ph2CHCOPh
detected by GC-MS (<5%)
*Reaction conducted after a pre-electrolysis (see text)
Scheme 2
On the basis of a possible effect of the geminal diphenyl
substitution on the stability of 2, we replaced dichlo-
rodiphenylmethane by benzal chloride as reagent, and
found that, in contrast with the previous reaction condi-
SYNTHESIS 2004, No. 3, pp 0389–0400
Advanced online publication: 13.01.2004
DOI: 10.1055/s-2004-815915; Art ID: Z16103SS.pdf
© Georg Thieme Verlag Stuttgart · New York
x
x
.
x
x
.2
0
0
4

390
S. Oudeyer et al.
PAPER
* Fe (anode)
Ni (cathode)
I = 0.2 A, 6 h
Ph
Ph
Ph
reduction
PhCHO
Ph
Ph
Ph2CCl
Ph2CCl2
2
1) 1,2-addition
5
+
PhCHCl2
10 mmol
PhCHO
O
O
2) SN
i
DMF/pyridine
(45mL/5mL)
isolated yield: 57%
20 mmol
isolated yield: 40%
-5 °C>T>-10 °C
Ph2C=CPh2
*Reaction conducted after a pre-electrolysis (see text)
Scheme 4
Scheme 3
In contrast, when the aldehyde is first reduced, the occur-
rence of the radical anion, which is clearly evidenced by
the formation of pinacols as the main by-products, likely
leads to the oxirane through electron transfer to the gem-
dihalide followed by a further reduction of the -chlo-
robenzyl radical; the ensuing formation of the oxirane can
be explained by 1,2-addition followed by SNi (Pathway
A). An alternative route involving the formation of the di-
anion from benzaldehyde (Pathway B) is less likely, inas-
much as this dianion would be quite a basic species
(Scheme 5).
tions, this reaction is best conducted, with respect to the
yield, with 2 equivalents of the aldehyde and at 0.2 A
(Scheme 3). It is also worth mentioning that the main by-
products are the mixture of (R*,R*)- and meso-hydroben-
zoins.
The differences between these two reactions can be ac-
counted for by the comparison of the reduction potential
of the reagents (Table 1).
Table 1 Reduction Potential of Some Reagents
a
a
PhCHOb
–1.95
PhCHCl2
In summary, we can have two types of process according
to the relative reduction potential of the two reagents in-
volved (Scheme 6). Below, and in Tables 2 and 3, Process
A and Process B refer, respectively, to the reactions where
the halo compound or the carbonyl compound is first re-
duced. In Process B, the use of 2 equivalents of carbonyl
compound, though not logical, at first, since it favours the
pinacol formation, allows, however, at a 0.2 A current in-
tensity, a better efficiency of the reaction. In addition, pi-
nacols are more easily separated from oxiranes than
hydrocarbons derived from gem-dihalo compounds.
Ph2CCl2
–1.78
E (V/SCE)
–2.2
a Ref.2
b Ref.26
Indeed, benzaldehyde is less easily reduced than dichlo-
rodiphenylmethane, but more easily than benzal chloride.
This may, therefore, involve different reaction mecha-
nisms. This may also explain the difference in the nature
of the by-products, i.e. dimerisation products of the halo
compounds in the former case, and of the aryl aldehydes
in the latter.
The oxiranes prepared from benzal chloride and a variety
of carbonyl compounds by either Process A or B are listed
in Table 2.
Thus, in the case of dichlorodiphenylmethane, the activa-
tion of the gem-dichloro compound would be the main
route (Scheme 4).
* Fe (anode)
Ni (cathode)
4-12 h
R'
Ph
R
RCOR' + PhCHCl2
DMF/pyridine
(45mL/5mL)
-5 °C>T>-10 °C
O
Process A: 10 mmol + 20mmol, I = 0.1 A
Process B: 20 mmol + 10mmol, I = 0.2 A
isolated yields:
10 - 70%
*Reactions conducted after a pre-electrolysis (see text)
Scheme 6
Scheme 5
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

PAPER
Epoxide Formation by Coupling between Aldehydes or Ketones and Dichloro Compounds
391
Aryl aldehydes are converted into 2-aryl-3-phenylox- the corresponding 2,2,3-trisubstituted oxiranes: yields are
iranes in medium to good isolated yields (Table 2, entries even higher than with aryl aldehydes (Table 2, entries 14–
1 to 9). There is no great influence of the substituent on the 18) and the cyano group does not impede the reaction of
aromatic aldehyde. However, the reaction is prevented by p-cyanoacetophenone (Table 2, entry 15). Finally, yields
a cyano group on the ring (Table 2, entry 10). Aliphatic al- are low from acyclic ketones (Table 2, entries 19 and 20),
dehydes are also interestingly transformed into the corre- while cyclic ketones are slightly more reactive and lead to
sponding oxiranes (Table 2, entries 11 and 12), if there is oxaspiroalkanes (Table 2, entries 21 and 22).
not much steric hindrance around the carbonyl (Table 2,
entry 13). Aryl ketones are efficiently transformed into
Table 2 Epoxide Formation by Indirect Electroreductive Coupling of Carbonyl Compounds and Benzal Chloride
Processa
Compound cis/trans
Yieldb (%) References
O
Entry
Carbonyl Compound
R'
R
No.
Ratio
Ph
5a,b,8,16
1
2
B
B
R = Ph,
R = H
5
25:75
40
CHO
38
R = 2-FC6H4,
R = H
6
7
30:70
30:70
30
F
CHO
F
35
3
B
R = 3-FC6H4,
R = H
28
CHO
24
4
5
6
B
B
B
R = 4-FC6H4,
R = H
8
9
40:60
48:52
22:78
30
F
CHO
15,24
R = 4-ClC6H4,
R = H
27
Cl
CHO
16,23
R = 2-MeC6H4,
R = H
10
36
CH3
CHO
3
7
B
R = 3-MeC6H4,
R = H
11
33:67
36
H3C
CHO
23,24
8
9
B
B
R = 4-MeC6H4,
R = H
12
13
47:53
34:66
32
H3C
CHO
17
R = 3-MeOC6H4,
R = H
29
H3CO
CHO
22
10
11
12
13
B
A
A
A
R = 4-NCC6H4,
R = H
14
15
16
17
–
traces
NC
CHO
O
14,18
R = Me(CH2)4,
R = H
33:66
37:63
20:80
34
H
O
6,7a
R = Me(CH2)5,
R = H
45
H
9
R = (Me)3C,
R = H
18
CH3
H3C
H3C
CHO
7b,c,9,10,11,21
14
A
R = Ph,
R = Me
18
56:44
54
O
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

392
S. Oudeyer et al.
PAPER
Table 2 Epoxide Formation by Indirect Electroreductive Coupling of Carbonyl Compounds and Benzal Chloride (continued)
Processa
Compound cis/trans
Yieldb (%) References
O
Entry
Carbonyl Compound
R'
R
No.
Ratio
Ph
15
A
R = 4-NCC6H4,
R = Me
19
70:30
35
43
New product
New product
O
NC
16
A
R = 2,4-Cl2C6H3,
R = Me
20
77:23
Cl
O
Cl
17
18
A
A
R = Ph,
R = Et
21
2
50:50
–
70
47
New product
O
6,7a
R = R = Ph
O
25
19
20
21
22
A
A
A
A
R = R = Et
22
23
24
25
–
–
–
–
11
10
32
20
O
R = R = Pr
New product
O
O
17
R = R = (CH2)4
R = R = (CH2)5
19,22
O
a Process A: DMF (45 mL), pyridine (5 mL), CuBr (144 mg, 1 mmol), NBu4Br (300 mg), Fe rod (anode), Ni foam (cathode), argon, I = 0.3 A,
15 min, –5 °C > T > –10 °C, RCOR (10 mmol) + PhCHCl2 (20 mmol), I = 0.1 A, –5 °C > T > –10 °C. Process B: DMF (45 mL), pyridine (5
mL), CuBr (144 mg, 1 mmol), NBu4Br (300 mg), Fe rod (anode), Ni foam (cathode), argon, I = 0.3 A, 15 min, –5 °C > T > –10 °C, RCOR (20
mmol) + PhCHCl2 (10 mmol), I = 0.2 A. –5 °C > T > –10 °C.
b Isolated yield.
Table 3 Epoxide Formation by Indirect Electroreductive Coupling of Carbonyl Compounds and Various Substituted Benzal Chlorides
Entry Carbonyl Compound
Subtituted
Processa
Epoxide
Benzal Chloride
Compound No. cis/trans Ratio Yieldb (%) References
1
2
3
4
B
B
B
B
26
27
28
6
35:65
37:63
25:75
43:57
45
32
25
44
New product
H3CO
H3CO
Cl
F
CHCl2
CHO
CHO
New product
CHCl2
CHCl2
New product
F
F
CHO
CHO
38
F
CHCl2
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

PAPER
Epoxide Formation by Coupling between Aldehydes or Ketones and Dichloro Compounds
393
Table 3 Epoxide Formation by Indirect Electroreductive Coupling of Carbonyl Compounds and Various Substituted Benzal Chlorides
(continued)
Entry Carbonyl Compound
Subtituted
Processa
Epoxide
Benzal Chloride
Compound No. cis/trans Ratio Yieldb (%) References
35
5
B
7
30:70
28
F
CHO
CHCl2
24
3
6
B
B
8
45:55
30:70
42
38
F
CHCl2
CHO
7
11
H3CO
CHO
CHCl2
23,24
15,24
17
8
B
B
B
12
9
38:62
27:73
27:73
30
40
32
H3C
CHCl2
CHO
9
Cl
CHCl2
CHO
10
13
H3C
CHO
CHCl2
22
11
B
A
A
14
15
29
30:70
35:65
50:50
32
30
40
CHO
NC
F
CHCl2
14,18
12
13
O
CHCl2
H
New product
New product
O
F
CHCl2
14
A
30
–
25
O
F
CHCl2
a Process A: DMF (45 mL), pyridine (5 mL), CuBr (144 mg, 1 mmol), NBu4Br (300 mg), Fe rod (anode), Ni foam (cathode), argon, I = 0.3 A,
15 min, –5 °C > T > –10 °C, RCOR (10 mmol) + ArCHCl2 (20 mmol), I = 0.1 A, –5 °C > T > –10 °C. Process B: DMF (45 mL), pyridine (5
mL), CuBr (144 mg, 1 mmol), NBu4Br (300 mg), Fe rod (anode), Ni foam (cathode), argon, I = 0.3 A, 15 min, –5 °C > T > –10 °C; RCOR (20
mmol) + ArCHCl2 (10 mmol), I = 0.2 A, – 5 °C > T > –10 °C.
b Isolated yield.
Substituted benzal chlorides have also been used in this already prepared from benzal chloride and substituted
reaction (Table 3). Few of them are commercially avail- benzaldehydes (see Table 2), there is no advantage in the
able. They were prepared according to the method we preparation of substituted benzal chlorides, since the
have published recently.27 They are less easily reduced yields are similar to those reported in Table 2.
than the aryl aldehydes, and the reactions have therefore
In connection with this work, the electrochemical Darzens
been conducted according to Process B (Table 3, entries 1
reactions carried out with , -dichloro esters by Sibille et
to 11). Yields are in the range of 25–45%. Of interest in
al.28 also leads readily to oxiranes without requiring the al-
this series is the preparation of new unsymmetrical ep-
kaline conditions of the classical Darzens reaction. The
oxides: 2,3-diaryloxiranes (Table 3, entries 1 to 3), 2-aryl-
facile work-up, the simplicity of these one pot electrolyses
1-oxaspiroalkanes (Table 3 entry 14), and 2-alkyl-2,3-di-
and the large range of characterized oxiranes (2,3-diary-
aryloxiranes (Table 3, entry 13). Also, the preparation of
loxiranes, 2-alkyl-3-aryloxiranes, 2-alkyl-2,3-diarylox-
2-aryl-3-phenyloxiranes having an electron-withdrawing
iranes, 2-aryl-1-oxaspiroalkanes) compensate the
group (CN) on the aryl ring (Table 3, entry 11) can be per-
moderate isolated yields thus obtained. We are now inves-
formed when the cyano group is on the halo compound.
tigating the preparation of aziridines by the same electro-
Finally, this can also be applied to the synthesis of 2-
chemical process from benzal chlorides and imines as
alkyl-3-aryloxiranes (Table 3, entry 12). For the other re-
reagents.
actions (Table 3, entries 4 to 10), which lead to products
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

394
S. Oudeyer et al.
PAPER
2-(2,4-Dichlorophenyl)-2-methyl-3-phenyloxirane (20)
Anal. Calcd for: C, 64.54; H, 4.83; O, 5.73. Found: C, 64.58; H,
4.52; O, 5.99.
Mps were determined with an Electrothermal IA 9100 digital mp
1
apparatus. H, 13C, 19F, NMR spectra were recorded on a Bruker
AC-200 (200, 50, 188 MHz, respectively) or a Bruker AM-300
(300, 75, 282 MHz, respectively) spectrometers. Mass spectra
(electron impact) were obtained on a GCQ Thermoquest spectrom-
eter coupled to a Finigan-GCQ, fitted with a DB 5MS capillary col-
umn. High-resolution mass spectral analyses and elemental
analyses were carried out at Service Central d’Analyse du CNRS,
Vernaison, France. Gas chromatography was performed on a Vari-
an 3300 chromatograph fitted with a SIL-5 CP capillary column.
Solvents and chemicals were used as received. The XC10 Fe rod
(iron with 0.1% of carbon) and the nickel foam are respectively pur-
chased from Weber Métaux and Nitech.
2-Ethyl-2,3-diphenyloxirane (21)
(EI-HRMS): m/z calcd for C16H16O (M)+: 224.1201; found:
224.1204.
3-Phenyl-2,2-dipropyloxirane (23)
(EI-HRMS): m/z calcd for C14H20O (M)+: 204.1514; found:
204.1520.
2-Phenyl-1-oxaspiro[2.4]heptane (24)
(EI-HRMS): m/z calcd for C12H14O (M)+: 174.1045; found:
174.1049.
Indirect Electrolysis with Fe Anode in the Presence of CuBr
(Processes A and B)
2-(4-Chlorophenyl)-3-(3-methoxyphenyl)oxirane (26)
(EI-HRMS): m/z calcd for C15H13ClO2 (M)+: 260.0104; found:
260.0697.
The reactions were conducted in an undivided cell fitted with an Fe
rod as the anode and a nickel foam as the cathode (area ca. 40 cm2).
A solution of CuBr (144 mg, 1 mmol) and NBu4Br (300 mg) in
DMF (45 mL) and pyridine (5 mL) was electrolysed at constant cur-
rent intensity (0.3 A) for 15 min at –5 °C > T > –10 °C. Then, the
aldehyde or the ketone (10 mmol) and the benzal chloride (20
mmol) were added and electrolysed (0.1 A) until the consumption
of the carbonyl compound (8–12 h, Process A); or the aryl aldehyde
(20 mmol) and the benzal chloride (10 mmol) were added and elec-
trolysed (0.2 A) until the consumption of the benzal chloride (4–8
h, Process B). The DMF was evaporated under reduced pressure.
The crude product was poured into a mixture of aq HCl (1 M; 50
mL) and Et2O (50 mL). The layers were separated and extracted
with Et2O (3 portions of 25 mL). The combined Et2O extracts were
washed with sat. aq (NaHCO3) and with brine, dried (Na2SO4), and
evaporated. Products were isolated by flash column chromatogra-
phy (silica gel 230–400 mesh; pentane–CH2Cl2).
2-(4-Fluorophenyl)-3-(3-methoxyphenyl)oxirane (27)
Anal. Calcd for: C, 73.76; H, 5.28; F, 7.78. Found: C, 73.57; H,
5.28; F, 7.48.
2-(2-Fluorophenyl)-3-(4-fluorophenyl)oxirane (28)
(EI-HRMS): m/z calcd for C14H10F2O (M)+: 232.0699; found:
232.0710.
2-Ethyl-3-(4-fluorophenyl)-2-phenyloxirane (29)
EI-HRMS: m/z calcd for C16H15FO (M)+: 242.1107; found:
242.1110.
2-(4-Fluorophenyl)-1-oxaspiro[2.5]octane (30)
(EI-HRMS): m/z calcd for C13H15FO (M)+: 206.1107; found:
206.1113.
2-(4-Cyanophenyl)-2-methyl-3-phenyloxirane (19)
(EI-HRMS): m/z calcd for C16H13NO (M)+: 235.0997; found:
235.0988.
Spectral data are given in Tables 4 and 5.
CAS registry numbers can be provided by the authors.
Table 4 Spectral Data for Epoxides 2, 5, 9–26
Product
No. IR (NaCl)
(cm–1)
1H NMR (200 MHz,
CDCl3) , J (Hz)
13C NMR (50.32 MHz,
CDCl3)
MS:
m/z (M+·) (% > 20)
2a 3089, 3065, 7.4–7.0 (m, 15 H), 4.3 (s, 1 141.1, 135.9, 135.6, 129.4, 272 (27), 271 (39), 166 (38),
3033, 2977, H)
2931, 1601,
1495, 1449,
1279, 1263,
1176, 1077,
1030, 940–
882
128.5, 128.0, 127.9, 127.8, 165 (100)
127.7, 127.0, 126.5, 68.8,
68.2
O
5a 3091, 3067, cis: 7.2–7.0 (m, 10 H), 4.3 cis: 134.4, 127.8, 127.7,
cis: 196 (40), 195 (76), 178 (39),
3034, 2989, (s, 2 H)
2930, 2895, trans: 7.4–7.2 (m, 10 H),
1952-1653, 3.9 (s, 2 H)
1604, 1496,
126.9, 59.8
168 (27), 167 (100), 165 (36),
trans: 137.2, 129.0, 128.5, 152 (21), 89 (39)
125.5, 62.8 trans: 196 (47), 195 (81), 178
O
(42), 168 (30), 167 (100), 165
(32), 152 (22), 89 (34)
1453, 1414,
1309, 1283,
1176, 1071,
1028, 873–
798
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

PAPER
Epoxide Formation by Coupling between Aldehydes or Ketones and Dichloro Compounds
395
Table 4 Spectral Data for Epoxides 2, 5, 9–26 (continued)
Product
No. IR (NaCl)
(cm–1)
1H NMR (200 MHz,
CDCl3) , J (Hz)
13C NMR (50.32 MHz,
CDCl3)
MS:
m/z (M+·) (% > 20)
9a 3090, 3068, cis: 7.2–7.0 (m, 9 H), 4.3
cis: 136.6, 135.6, 133.9,
cis: 230 (27), 203 (26), 201 (73),
Cl
3036, 2991, (d, 1 H, J = 4.2), 4.2 (d, 1 133.3, 132.9, 128.1, 127.9, 195 (100), 178 (25), 167 (60),
2927, 2854, H, J = 4.2), AB system 126.7, 59.5, 58.9 166 (64), 165 (72), 89 (41)
1603, 1493, /J = 2.8) trans: 136.9, 135.8, 134.2, trans: 230 (34), 214 (42), 212
1459, 1428, trans : 7.35–7.0 (m, 9 H), 128.9, 128.7, 128.6, 127.0, (20), 203 (31), 202 (20), 201
(
O
1397, 1291, 3.75 (d, 1 H, J = 1.7), 3.7 125.6, 63.0, 62.2
(100), 195 (92), 194 (22), 179
(43), 178 (43), 167 (72), 166
(88), 165 (89), 89 (38)
1275, 1174, (d, 1 H, J = 1.7), AB sys-
1092, 1014, tem ( /J = 2,6)
902–888,
847, 824
10a 3060, 3040, cis: 7.25–7.0 (m, 9 H), 4.4 cis: 135.7, 134.5, 132.5,
cis: 210 (19), 195 (100), 181
CH3
O
2980, 1600, (d, 1 H, J = 4.3), 4.3 (d, 1 129.3, 127.6, 126.5, 125.2, (58), 167 (46), 166 (43), 165
1480, 1460, H, J = 4.3), 2.2 (s, 3 H), 125.6, 59.6, 59.1, 18.7 (33), 78 (22)
1260
AB system ( /J = 1.9)
trans : 7.6–7.3 (m, 9 H),
trans: 145.4, 137.3 135.6, trans: 210 (17), 195 (100), 194
129.8, 128.5, 127.7, 126.1, (20), 181 (63), 179 (23), 178
4.2 (d, 1 H, J = 1.9), 3.9 (d, 125.4, 123.9, 61.8, 60.9,
(21), 167 (47), 166 (41), 165
(38), 78 (20)
1 H, J = 1.9), 2.5 (s, 3 H)
AX system ( /J = 26.3)
18.8
11a 3140, 3060, cis: 7.4–7.0 (m, 9 H), 4.4
cis: 137.7, 137.4, 134.3,
cis: 210 (52), 209 (53), 195 (81),
CH3
3020, 2980, (d, 1 H, J = 4.3), 4.3 (d, 1 129.9, 128.4, 127.7, 126.9, 194 (25), 192 (44), 182 (24),
2920, 1620, H, J = 4.3), 2.3 (s, 3 H),
1450, 1280 AB system ( /J = 1.5)
trans : 7.3–7.0 (m, 9 H),
126.1, 123.9, 60.0, 59.6,
21.5
trans: 138.1, 137.0, 136.9, (24), 77 (20)
181 (100), 178 (21), 167 (60),
166 (80), 165 (60), 89 (27), 78
O
3.75 (d, 1 H, J = 1.8), 3.7
128.9, 128.3, 128.1, 125.8, trans: 210 (55), 209 (53), 195
(d, 1 H, J = 1.8), 2.25 (s, 3 125.3, 122.5, 62.7, 62.3,
(70), 194 (23), 192 (40), 182
(27), 181 (100), 178 (20), 167
(68), 166 (87), 165 (70), 89
(25), 78 (22)
H), system AB (
/
21.1
J = 3.2)
12a 3060, 3020, cis: 7.2–6.8 (m, 9 H), 4.2
2980, 1610, (s, 2 H), 2.1 (s, 3 H)
1500, 1250 trans : 7.3–7.1 (m, 9 H),
3.7 (d, 1 H, J = 1.8), 3.75
cis: 136.9, 134.4, 131.1,
128.8, 128.3, 127.6, 127.3, 192 (26), 182 (21), 181 (100),
126.7, 126.6, 59.7, 59.5,
21.0
trans: 138.1, 137.0, 136.9, (87), 192 (20), 182 (31), 181
cis: 210 (34), 209 (33), 195 (97),
H3C
167 (40), 166 (50), 165 (41)
trans: 210 (40), 209 (29), 195
O
(d, 1 H, J = 1.8), 2.2 (s, 3
H), AB system (
/
128.9, 128.3, 128.1, 125.8, (100), 167 (32), 166 (45), 165
J = 2.7)
125.3, 122.5, 62.7, 62.6,
21.1
(36)
13a 3089, 3066, cis: 7.3–6.6 (m, 9 H), 4.3
cis: 158.1, 136.0, 134.3,
cis: 226 (100), 225 (61), 211
OCH3
3034, 3005, (d, 1 H, J = 4.3), 4.2 (d, 1 128.8, 127.8, 127.5, 126.8, (27), 210 (24), 209 (34), 208
2963, 2942, H, J = 4.3), 3.6 (s, 3 H),
2837, 1604, AB system ( /J = 1.55)
1492, 1456, trans : 7.6–7.5 (m, 6 H),
119.7, 113.5, 111.9, 59.6, (81), 197 (69), 195 (41), 194
55.1, 54.9 (31), 193 (24), 182 (32), 167
trans: 160.0, 138.9, 137.1, (23), 165 (66)
O
1436, 1406, 7.2–7.1 (m, 3 H), 4.1 (s, 2 129.7, 128.6, 128.4, 125.6, trans: 226 (70), 225 (68), 211
1365, 1319, H), 4.0 (s, 3 H)
1287, 1201,
1154, 1076,
118.0, 114.2, 110.5, 62.8, (25), 210 (40), 209 (40), 208
55.3, 55.2
(66), 197 (100), 195 (51), 194
(30), 193 (20), 182 (35), 167
(21), 165 (62), 153 (21)
1043, 934–
784
14a 3091, 3068, mixture of cis/trans 25:75: mixture of cis/trans 25:75: cis: 221 (51), 220 (46), 203 (23),
NC
3036, 2992, cis, [trans]: 7.5–7.0 (m, 9 cis, [trans]:140.0, 133.4,
2928, 2856, H cis + 9 H trans), 4.3 (d, [142.5; 136.2], 132.5,
193 (76), 192 (100), 191 (23),
165 (61), 90 (20), 89 (46)
2228, 1953– 1 H, J = 4), 4.25 (d, 1 H,
1702, 1611, J = 4), [3.8 (d, 1 H,
1585, 1498, J = 1.4), 3.7 (d, 1 H,
1457, 1427, J = 1.4)], cis: AB system
132.3, 131.6, 128.7, 127.5, trans: 221 (52), 220 (38), 203
126.7, 126.2, 125.6, 118.6, (20), 193 (74), 192 (100), 190
111.3, [111.9], 61.9, 61.7, (21), 165 (60), 130 (20), 89 (41)
[63.3, 63.1]
O
1364, 1345,
(
/J = 3.2); [trans: AX
1316, 1280, system ( /J = 11.2)]
1177, 1110,
1070, 833
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

396
S. Oudeyer et al.
PAPER
Table 4 Spectral Data for Epoxides 2, 5, 9–26 (continued)
Product
No. IR (NaCl)
(cm–1)
1H NMR (200 MHz,
CDCl3) , J (Hz)
13C NMR (50.32 MHz,
CDCl3)
MS:
m/z (M+·) (% > 20)
15a 3090, 3067, cis: 7.5–6.9 (m, 5 H), 4.2
cis: 135.7, 127.9, 127.2,
cis: 190 (12), 161 (24), 133 (29),
129 (32), 119 (21), 117 (24),
108 (82), 107 (67), 106 (100),
3032, 2930, (d, 1 H, J = 4.2), 3.35 (dt, 1 126.3, 59.3, 57.2, 32.2,
2860, 1604, H, J = 4.2, 5.3), 1.9–1.8 31.3, 26.5, 22.3, 13.8
1585, 1497, (m, 2 H), 1.7–1.3 (m, 6 H), trans: 137.9, 128.3, 127.8, 105 (96), 104 (35), 93 (22), 92
O
1456, 1379, 1.2–0.9 (m, 3 H)
125.4, 63.0, 58.4, 32.2,
31.5, 25.5, 22.5, 13.9
(23), 91 (71), 90 (72), 89 (43),
80 (25), 79 (61), 78 (92), 77 (51)
trans: 190 (11), 161 (27), 133
(27), 130 (40), 117 (24), 108
(49), 107 (96), 106 (100), 105
(79), 104 (33), 93 (27), 92 (39),
91 (69), 90 (35), 89 (46), 88
(24), 82 (24), 81 (21), 79 (57),
78 (50), 77 (35)
1312, 1273, trans: 7.5–6.9 (m, 5 H),
1241, 1199, 3.75 (d, 1 H, J = 1.95), 3.1
1072, 1027, (dt, 1 H, J = 1.95, 5.3),
920–877
1.9–1.8 (m, 2 H), 1.7–1.3
(m, 6 H), 1.2–0.9 (m, 3 H)
16a 3160, 3080, cis: 7.25–7.1 (m, 5 H), 3.9 cis: 135.6, 128.2, 127.1,
3060, 3020, (d, 1 H, J = 4.25), 2.8 (dt, 1 126.2, 59.2, 57.2, 32.1,
cis: 133 (19), 107 (63), 105
(100), 91 (53), 89 (29), 79 (83),
2990 to
2840 (br),
H, J = 4.25, 5.4), 1.6–1.05 31.4, 28.9, 26.4, 22.2, 13.8 77 (24)
(m, 10 H), 0.8–0.7 (m, 3 H) trans: 138.0, 128.4, 127.9, trans: 161 (11), 133 (20), 107
O
1600, 1580, trans: 7.3–7.1 (m, 5 H), 3.5 125.5, 63.2, 58.6, 32.3,
1500, 1250 (d, 1 H, J = 2), 2.85 (dt, 1 31.7, 29.1, 25.9, 22.5, 14
H, J = 2, 5.4), 1.6–1.1 (m,
(61), 106 (10), 105 (100), 91
(53), 89 (29), 79 (73), 77 (24)
10 H), 0.8–0.7 (m, 3 H)
17a 3160, 3100, cis: 7.2–7.1 (m, 5 H), 3.95 mixture of cis/trans: 138.1, cis: 176 (7), 120 (28), 107 (27),
3080, 3040, (d, 1 H, J = 4.6), 2.8 (d, 1 136.4 128.2, 127.8, 126.4, 91 (37), 90 (11), 89 (34), 79
CH3
H3C
H3C
2990–2880, H, J = 4.6), 0.6 (s, 9 H)
125.3, 70.8, 70.6, 55.2,
(49), 77 (31), 70 (58), 55 (100)
trans: 176 (20), 120 (35), 107
(31), 91 (50), 89 (33), 79 (50),
77 (29), 70 (70), 55 (100)
1610, 1590, trans: 7.2–7.1 (m, 5 H), 3.6 55.1, 32.0, 31.1, 27.1,
O
1580, 1440, (d, 1 H, J = 2.2), 2.6 (d, 1 27.0, 26.7, 25.8, 25.6
1390, 1370, H, J = 2.2), 0.9 (s, 9 H)
1250, 1190,
1100
18a 3090, 3065, cis: 7.2–6.9 (m, 10 H), 4.0 cis: 138.4, 135.6, 128.8,
cis: 210 (70), 209 (84), 195 (34),
3030, 2990, (s, 1 H), 1.7 (s, 3 H)
2935, 2890, trans: 7.6–7.4 (m, 10 H),
1600, 1585, 4.0 (s, 1 H), 1.6 (s, 3 H)
1495, 1280
128.3, 127.9, 127.7, 127.4, 194 (21), 167 (100), 166 (27),
127.1, 127.0, 126.6, 66.1, 165 (34), 78 (27)
65.6, 25.8
trans: 210 (64), 209 (100), 195
O
trans: 142.3, 135.9, 128.4, (61), 167 (94), 166 (37), 165
128.1, 127.6, 127.4, 126.4, (28), 77 (24)
125.1, 67.0, 62.9, 16.6
19 3089, 3066, cis: 7.6–6.9 (m, 9 H), 4.2
mixture of cis/trans: 143.9, cis: 235 (64), 234 (36), 220 (83),
NC
3032, 2975, (s, 1 H), 1.8 (s, 3 H)
143.8, 135.1, 134.7, 132.4, 217 (26), 193 (100), 192 (86),
2929, 2866, trans: 7.6–6.9 (m, 9 H), 3.9 131.8, 128.4, 128.0, 127.8, 165 (33), 129 (28), 128 (26),
2231, 1952- (s, 1 H), 1.4 (s, 3 H)
1685, 1609,
1497, 1452,
1404, 1379,
1262, 1070
126.6, 126.3, 126.1, 118.7, 102 (32), 89 (23)
O
111.4, 111.1, 67.2, 65.7,
65.5, 62.6, 24.9, 16.7
trans: 235 (65), 234 (26), 220
(89), 217 (21), 193 (100), 192
(82), 165 (29), 129 (34), 128
(30), 102 (34)
20 3060, 3040, cis: 7.45–6.9 (m, 8 H), 4.1 cis: 135.6, 134.6, 133.8,
cis: 280 (19), 278 (28), 245 (29),
Cl
2980, 2920, (s, 1 H), 1.7 (s, 3 H)
1590, 1560, trans: 7.5–6.9 (m, 8 H),
1490, 1250 3.95 (s, 1 H), 1.3 (s, 3 H)
132.8, 130.6, 129.9, 128.3, 243 (86), 237 (35), 235 (49),
127.5, 126.9, 126.4, 65.9, 174 (32), 172 (49), 139 (34),
65.4, 23.5
137 (100), 102 (35)
O
Cl
trans: 139.9, 135.6, 134.1, trans: 280 (12), 278 (20), 245
132.8, 130.8, 129.6, 129.0, (26), 243 (84), 237 (32), 235
127.8, 127.0, 126.7, 65.7, (46), 174 (30), 172 (48), 139
64.7, 17.4
(31), 137(100), 102 (31)
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

PAPER
Epoxide Formation by Coupling between Aldehydes or Ketones and Dichloro Compounds
397
Table 4 Spectral Data for Epoxides 2, 5, 9–26 (continued)
Product
No. IR (NaCl)
(cm–1)
1H NMR (200 MHz,
CDCl3) , J (Hz)
13C NMR (50.32 MHz,
CDCl3)
MS:
m/z (M+·) (% > 20)
21 3060, 3040, cis: 7.2–7.0 (m, 10 H), 4.15 cis: 136.9, 135.7, 127.8,
cis: 224 (29), 223 (42), 195 (44),
2980, 2940, (s, 1 H), 2.25–2.1 (m, 1 H), 127.7, 127.6, 127.3, 127.0, 167 (100), 165 (20), 117 (52),
2900, 1590, 2.0–1.8 (m, 1 H), 1.0 (t, 3 126.5, 69.9, 64.5, 31.9, 9.1 115 (30)
1560, 1490, H, J = 7.4)
1250 trans: 7.4–7.1 (m, 10 H),
trans: 140.5, 135.8, 128.3, trans: 224 (25), 223 (36), 195
128.0, 127.5, 127.3, 126.3, (53), 192 (59), 168 (21), 167
O
3.9 (s, 1 H), 1.9–1.7 (m, 1 125.9, 67.4, 66.9, 22.9, 9.0 (100), 165 (21), 117 (69), 115
H), 1.5–1.3 (m, 1 H), 0.8 (t,
(34), 91 (28)
3 H, J = 7.4)
22 3091, 3067, 7.3–7.1 (m, 5 H), 3.8 (s, 1 136.6, 127.9, 127.1, 126.3, 176 (18), 147 (24), 119 (20),
3034, 2989, H), 1.75–1.5 (m, 2 H), 1.4– 67.4, 63.4, 27.2, 21.6, 8.2, 105 (22), 91 (100), 89 (22), 79
2930, 2895, 1.1 (m, 2 H), 0.9 (t, 3 H,
1952-1653, J = 7.5), 0.7 (t, 3 H,
1604, 1496, J = 7.5)
1453, 1414,
8.0
(24), 77 (20)
O
1309, 1283,
1176, 1071,
1028, 873–
798
23 3089, 3065, 7.3–7.1 (m, 5 H), 3.8 (s, 1 136.4, 127.6, 126.9, 126.1, 204 (10), 133 (20), 118 (80),
3033, 2963, H), 1.8–1.0 (m, 8 H), 0.9 (t, 65.8, 63.4, 37.0, 30.4, 117 (25), 91 (100)
2930, 2845, 3 H, J = 7.5), 0.7 (t, 3 H,
18.1, 17.9, 14.0, 13.8
1604, 1515, J = 7.5)
1460, 1378,
O
1226
24 3080, 3060, 7.4–7.0 (m, 5 H), 3.9 (s, 1 137.1, 128.0, 127.3, 126.1, 174 (79), 173 (63), 146 (55),
2980, 2940, H), 1.7–1.1 (m, 8 H)
1450, 1600,
1580, 1250
72.3, 63.0, 33.4, 28.2,
25.1, 24.9
145 (45), 143 (21), 141 (45),
131 (47), 130 (23), 129 (30),
128 (49), 118 (34), 117 (52),
115 (28), 105 (36), 91 (100), 90
(45), 89 (88), 79 (31), 77 (30),
67 (24)
O
25a 3080, 3060, 7.2–7.15 (m, 5 H), 3.7 (s, 1 136.3, 127.8, 127, 126.2,
188 (45), 170 (37), 142 (24),
141 (23), 129 (22), 97 (27), 91
(100), 79 (28), 77 (23)
2980, 1600, H), 1.75–1.1 (m, 10 H)
1580, 1250
65.2, 64.3, 35.3, 28.3,
25.4, 25.2, 24.4
O
26 3054, 3005, cis: 7.1–7.0 (m, 4 H), 6.7– cis: 159.2, 135.6, 133.4,
cis: 260 (22), 242 (28), 231 (41),
OCH3
2965, 2941, 6.6 (m, 4 H), 4.25 (d, 1 H, 133.0, 129.0, 128.2, 128.1, 226 (21), 225 (100), 210 (22),
2838, 1603, J = 4.3), 4.2 (d, 1 H, 119.2, 113.5, 112.2, 59.7, 196 (42), 194 (26), 181 (30),
1587, 1493, J = 4.3), 3.6 (m, 3 H), AB 59.1, 55.1
1467, 1439, system ( /J = 1.95) trans: 59.8, 138.3, 135.5,
Cl
165 (26), 89 (20)
trans: 260 (25), 244 (23), 233
O
1424, 1336, trans: 7.4–7.3 (m, 5 H), 7– 133.9, 129.5, 128.6, 126.7, (20), 231 (62), 225 (100), 210
1319, 1289, 6.9 (m, 3 H), 3.9–3.8 (m, 5 117.8, 114.1, 110.3, 62.6, (21), 197 (20), 196 (55), 194
1274, 1261, H)
1149, 1092,
1048, 1015,
930–785
61.8, 55.1
(31), 182 (20), 181 (38), 165
(32), 89 (21)
a Compounds gave satisfactory IR, NMR, mass spectrum according to the spectral data references: 2 (1H NMR,29 MS29); 5 (1H NMR,30 13
C
NMR cis,31 trans,32 MS cis,31 trans32); 9 (IR,22 1H NMR cis,33 trans,24,34 13C NMR trans,34); 10 (1H NMR cis,16 trans16); 11 (MS35); 12 (1H NMR
cis,36 trans,37 13C NMR trans,37 MS cis,36 trans36); 13 (MS35); 14 (MS35); 15 (1H NMR cis18); 16 (1H NMR cis6); 17 (1H NMR cis,9d trans9d); 18
(1H NMR cis,7btrans,7b,22 13C NMR trans22); 25 (IR,22 1H NMR,22 13C NMR22).
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

398
S. Oudeyer et al.
PAPER
Table 5 Spectral Data for Mono or Difluoro Epoxides 6–8, 15, 28–30
Product
Comp. IR (NaCl)
No.
1H NMR
(200 MHz, CDCl3) MHz, CDCl3)
, J (Hz) , J (Hz)
19F NMR (188
13C NMR
(50.32 MHz, CDCl3)
, J (Hz)
MS
(cm–1)
m/z (M+·) (% > 20)
6a
3090, 3070, cis: 7.3–6.7 (m, 9 cis: –118.5 (dt, cis: 160.8 (d, J = 246),
3040, 2990, H), 4.4 (d, 1 H, J = 6.6, 10.5)
2930, 1600, J = 4.3), 4.3 (d, 1 trans: –120.6
cis: 214 (49), 213
134.1, 129.0 (d, J = 7.8), (39), 196 (36), 194
F
128.7, 127.7, 127.5,
(12), 186 (59), 185
(100), 183 (20), 166
1580, 1500, H, J = 4.3), AB
(dt, J = 6.2,
126.5, 123.3 (d, J = 3),
O
1250
system (
/
10.9)
114.6 (d, J = 20.3), 58.9, (24), 165 (90)
J = 2.2)
55.8 (d, J = 6)
trans: 214 (60), 213
trans: 7.3–6.9 (m,
9 H), 4.05 (d, 1 H,
J = 1.8), 3.75 (d,
1 H, J = 1.8), AX
trans: 161.6 (d, J = 248), (41), 196 (36), 186
136.8, 129.6 (d, J = 8.2), (66), 185 (100), 183
129.5, 128.7, 128.6,
125.9, 125.7, 124.5 (d,
J = 3.3), 115.3 (d,
J = 21.1), 62.2, 57.8 (d,
J = 5.7)
(21), 166 (25), 165
(94)
system (
/
J = 33.9)
7a
3090, 3065, cis: 7.25–6.6 (m, cis: –113 (dt,
3030, 2990, 9 H), 4.3 (d, 1 H, J = 5.6, 8.3)
2930, 1600, J = 4.3), 4.2 (d, 1 trans: –112.3
cis: 162.5 (d, J = 245.6), cis: 214 (33), 213
137.2 (d, J = 7.8), 133.9, (49), 196 (54), 186
129.4 (d, J = 8.3), 127.9, (32), 185 (100), 183
F
1520, 1460, H, J = 4.3), AB
(m)
127.7, 126.8, 122.6 (d,
J = 2.8), 114.5 (d,
J = 21.3), 113.9 (d,
J = 22.6), 59.9, 59.2
trans: 163.0 (d,
J = 246.4), 139.7 (d,
J = 7.5), 36.5, 130, 128.4, (96), 89 (21)
125.3, 121.2, 115.0 (d,
(36), 165 (88), 89
(26)
trans: 214 (47), 213
(48), 197 (24), 196
(54), 186 (36), 185
(100), 183 (33), 165
1260
system (
/
O
J = 2.1)
trans: 7.3–6.8 (m,
9 H), 3.7 (d, 1 H,
J = 1.8), 3.0 (d, 1
H, J = 1.8), AB
system (
/
J = 3.3)
J = 21.2), 112.1 (d,
J = 21.6), 62.7, 61.8
8a
3091, 3069, cis: 7.3–6.9 (m, 9 cis: –114 (tt,
3036, 2991, H), 4.25 (d, 1 H, J = 5, 8.3)
2928, 2894, J = 4.3), 4.2 (d, 1 trans: –113.2
1604, 1517, H, J = 4.3), AB
cis: 162.1 (d, J = 246),
134.0, 130.1, 128.4 (d,
J = 8.1), 127.8, 127.5,
cis: 214 (33), 213
(49), 196 (33), 186
(26), 185 (100), 183
F
(tt, J = 5.8, 8.8) 126.7, 114.7 (d, J = 21.5), (25), 165 (62)
O
1459, 1435, system (
/
59.6, 59.0
trans: 162.8 (d,
trans: 214 (37), 213
(44), 196 (35), 186
1228, 1156, J = 1.7)
1100, 1071, trans: 7.3–6.9 (m,
J = 246.8), 136.8, 132.9, (24), 185 (100), 183
1027, 1014, 9 H), 3.75 (d, 1 H,
128.6, 128.4, 127.2 (d,
J = 8.2), 125.5, 115.6 (d,
J = 21.6), 62.8, 62.3
(27), 165 (65)
940–870,
831
J = 1.8), 3.7 (d, 1
H, J = 1.8), AB
system (
/
J = 2.7)
15a
3037, 2932, mixture of cis/
2860, 1608, trans 35:65
1513, 1467, cis, [trans]: 7.3–
cis: –114.8 (tt,
J = 5.2, 7.7)
trans: –114.1
mixture of cis/trans
35:65:
cis: 208 (1), 125
(68), 123 (100), 109
(54), 108 (34), 107
(41), 103 (38), 97
(48)
trans: 208 (1), 125
(70), 123 (100), 109
(46), 108 (34), 107
F
cis, [trans]: [162.6 (d,
J = 245.7)], 162.2 (d,
J = 245.6), [133.8 (d,
J = 3)], 131.6, (cis +
trans): 128.0, 127.0,
[115.3 (d, J = 21.2)],
114.6, [63.1, 57.9], 59.3, (41), 103 (36), 97
56.7, (cis + trans): 32.2, (43)
31.6, 26.5, 25.5, 22.5,
1458, 1379, 7.0 (m, 8 H (cis + (tt, J = 5.3,
O
1296, 1224, trans)), 4.1 (d, 1
1156, 1094, H, J = 4.2), [3.6
1014, 920– (d, 1 H, J = 2.0)],
8.15)
860, 835
(br)
3.2 (dt, 1 H,
J = 4.2, 6), [2.9
(dt, 1 H, J = 2.0,
5.6)], 1.6–0.9 (m,
11 H cis + 11 H
trans)
22.4, 13.8
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

PAPER
Epoxide Formation by Coupling between Aldehydes or Ketones and Dichloro Compounds
399
Table 5 Spectral Data for Mono or Difluoro Epoxides 6–8, 15, 28–30 (continued)
Product
Comp. IR (NaCl)
No.
1H NMR
(200 MHz, CDCl3) MHz, CDCl3)
, J (Hz) , J (Hz)
19F NMR (188
13C NMR
(50.32 MHz, CDCl3)
, J (Hz)
MS
m/z (M+·) (% > 20)
(cm–1)
28
3060, 3040, cis: 7.3–6.7 (m, 8 cis: –114.3 (tt,
2980, 1610, H), 4.35 (d, 1 H, J = 4.5, 8.95),
1580, 1510, J = 4.2), 4.3 (d, 1 –118.6 (dt,
cis: 162.0 (d, J = 245.9), cis: 232 (31), 204
F
F
160.7 (d, J = 246.3),
129.6 (d, J = 3), 129.0,
128.6, 128.1, 127.9,
127.8, 123.2, 121.7,
(38), 203 (100), 183
(60), 108 (35), 107
(56)
1250
H, J = 4.2), AB
J = 5.6, 10.7)
trans: –112.9
O
system (
/
trans: 232 (35), 214
J = 2.7)
trans: 7.25–6.9
(m, 8 H), 4.0 (d, 1 J = 6.3, 11.2)
H, J = 1.6), 3.75
(d, 1 H, J = 1.6).
(tt, J = 5.3, 8.8), 121.4, 114.6 (d, J = 21.7), (20), 204 (36), 203
–120.5 (dt, 58.3, 55.5 trans: 162.8 (d, (100), 183 (58), 123
J = 246.9), 161.4 (d, (22), 108 (32), 107
J = 247.5), 132.3, 129.5, (54)
127.3, 125.7, 124.3,
AX system (
J = 34.4)
/
124.1, 115.5 (d, J = 21.7),
61.4, 57.0 (d, J = 6)
27
3055, 3003, cis: 7.2–6.6 (m, 8 cis: –114.4 (tt,
2965, 2941, H), 4.25 (d, 1 H, J = 5.2, 8.55)
2838, 1605, J = 4), 4.2 (d, 1 H, trans: –113.3
cis: 162.7 (d, J = 246.6), cis: 244 (80), 243
OCH3
159.1, 135.7, 130.1,
(47), 229 (21), 228
F
128.9, 128.5 (d, J = 8.1), (32), 227 (48), 226
1588, 1513, J = 4), 3.6 (3 H,
(tt, J = 5.1, 8.3) 119.2, 114.8 (d, J = 21.6), (89), 224 (27), 216
1493, 1467, m), AB system
113.4, 112.1, 59.7, 59.3, (22), 215 (100), 213
O
1440, 1319,
(
/J = 1.6)
55.0
(55), 212 (46), 211
(21), 200 (30), 184
1276, 1261, trans: 7.2–6.7 (m,
trans: 162.7 (d,
1239, 1146, 8 H), 3.7 (d, 1 H,
J = 246.5), 159.9, 138.5, (26), 183 (82), 172
132.8 (d, J = 3), 129.6, (21), 165 (31), 123
1049
J = 1.7), 3.9–3.8
(m, 4 H)
127.2 (d, J = 8.2), 117.9, (20), 107 (35)
115.5 (d, J = 21.7), 114.1, trans: 244 (56), 243
110.4, 62.7, 62.1, 55.1
(26), 229 (22), 228
(76), 227 (55), 226
(53), 215 (100), 213
(44), 212 (41), 200
(20), 197 (36), 185
(24), 184 (20), 183
(69), 165 (32)
29
3086, 3064, cis: 7.3–6.7 (m, 9 cis: –114.98 (tt, cis: 162.0 (d, J = 246.6), cis: 242 (33), 241
F
3031, 2974, H), 4.1 (s, 1 H),
2938, 2879, 2.25–2.05 (m, 1
J = 5.7, 8.2)
trans: –114.4
136.6, 131.5, 128.1,
128.0, 127.7, 127.1,
(45), 213 (44), 185
(100), 165 (26), 117
1952–1681, H), 1.95–1.8 (m, (m)
1600, 1510, 1 H), 1.0 (t, 3 H,
1447, 1357, J = 7.5)
114.6 (d, J = 21.6), 69.9, (56), 115 (24)
O
63.7, 31.7, 9.0
trans: 242 (37), 241
trans: 162.3 (d,
J = 246.0), 140.3, 131.6
(42), 213 (54), 185
(100), 165 (28), 117
1224, 1156, trans: 7.5–7.0 (m,
835
9 H), 3.95 (s, 1
H), 2.0–1.8 (m, 1
H), 1.6–1.4 (m, 1
H), 0.9 (t, 3 H,
J = 7.4)
(d, J = 3.1), 128.5, 128.1, (63), 115 (26)
127.5, 126.0, 115.1 (d,
J = 21.6), 67.6, 66.5,
22.9, 9.1
30
3100, 3060, 7.2–6.8 (m, 4 H), –114.9 (tt,
2960, 1600, 3.7 (s, 1 H), 1.8– J = 5.6, 8.0)
1580, 1250 1.0 (m, 10 H)
161.8 (d, J = 245.2),
131.8 (d, J = 3), 127.6 (d,
J = 7.9), 114.5 (d,
J = 21.5), 65.2, 63.6,
35.0, 28.0, 25.4, 25.1,
24.2
206 (22), 109 (100)
F
O
a Compounds give satisfactory IR, NMR, mass spectrum according to the spectral data references: 6 (1H NMR trans,38 13C NMR trans38); 7
(MS trans35); 8 (IR,25 1H NMR trans,25 MS trans35); 15 (IR,11, 1H NMR14).
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York

400
S. Oudeyer et al.
PAPER
(19) Johnson, C. R.; Mori, K.; Nakanishi, A. J. Org. Chem. 1979,
44, 2065.
(20) (a) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1962,
84, 867. (b) Corey, E. J.; Oppolzer, W. J. Am. Chem. Soc.
1964, 86, 1899.
(21) Hatch, M. J. J. Org. Chem. 1969, 34, 2133.
(22) (a) Aggarwal, V. K.; Abdel-Rahman, H.; Fan, L.; Jones, R.
V. H.; Standen, M. C. H. Chem.–Eur. J. 1996, 8, 1024.
(b) Aggarwal, V. K.; Alonso, E.; Hynd, G.; Lyndon, K. M.;
Palmer, M. J.; Porcelloni, M.; Studley, J. R. Angew. Chem.
Int. Ed. 2001, 40, 1430.
(23) Padwa, A.; Gasdaska, J. R. Tetrahedron 1988, 44, 4147.
(24) Zhong, K.; Shao, J.; Liu, C.; Lu, R. Synth. Commun. 1991,
21, 869.
(25) Shanklin, J. R.; Johnson, C. R.; Ollinger, J.; Coates, R. M. J.
Am. Chem. Soc. 1973, 95, 3429.
(26) Durandetti, M.; Périchon, J.; Nédélec, J.-Y. Tetrahedron
Lett. 1999, 40, 9009.
(27) Léonel, E.; Paugam, J. P.; Heintz, M.; Nédélec, J.-Y. Synth.
Commun. 1999, 29, 4015.
References
(1) Sengmany, S.; Léonel, E.; Paugam, J. P.; Nédélec, J.-Y.
Synthesis 2002, 533.
(2) Oudeyer, S.; Léonel, E.; Paugam, J. P.; Nédélec, J.-Y.
Tetrahedron 2003, 59, 1073.
(3) Lynch, B. M.; Pausacker, K. H. J. Chem. Soc. 1955, 1525.
(4) Gupta, K. C.; Nigam, R. K.; Srivastava, N. Indian Curr. Sci.
1984, 53, 191.
(5) (a) Heck, R. F. Org. React. 1982, 27, 345. (b) Sho, C. S.;
Uemura, S. J. Organomet. Chem. 1994, 465, 85.
(6) Bellucci, G.; Chiappe, C.; Cordoni, A. Tetrahedron:
Asymmetry 1996, 7, 197.
(7) (a) Lane, J. F.; Walters, D. R. J. Am. Chem. Soc. 1951, 73,
4234. (b) Shaap, A. P.; Siddiqui, S.; Prasad, G.; Palomino,
E.; Sandison, M. Tetrahedron 1985, 41, 2229.
(c) Simmamura, O.; Suzuki, H. Bull. Chem. Soc. Jpn. 1954,
27, 231.
(8) Cope, A. C.; Trumbull, P. A.; Trumbull, E. R. J. Am. Chem.
Soc. 1958, 80, 2844.
(9) (a) Tiffeneau, M.; Levy, J. Bull. Soc. Chim. Fr. 1931, 49,
1806. (b) Kayser, F. Ann. Chim. Paris 1936, 6, 144.
(c) Ogata, Y.; Tabushi, I. J. Am. Chem. Soc. 1961, 83, 3440.
(d) Lazzeretti, P.; Taddei, F.; Torre, G. Org. Magn.
Resonance 1973, 5, 385.
(10) Frohn, M.; Wang, Z. X.; Shi, Y. J. Org. Chem. 1998, 63,
6425.
(11) Zadok, E.; Amar, D.; Mazur, Y. J. Am. Chem. Soc. 1980,
102, 6370.
(12) Nishino, H.; Satoh, H.; Yamashita, M.; Kurosawa, K. J.
Chem. Soc., Perkin Trans. 2 1999, 1919.
(13) Comprehensive Organic Transformation, A Guide to
Functional Group Preparation; Larock, R. C., Ed.; VCH:
New York, 1989, 457.
(14) Yamada, T.; Takai, T.; Rhode, O.; Mukaiyama, T. Bull.
Chem. Soc. Jpn. 1991, 64, 2109.
(15) Cainelli, G.; Tangari, N.; Umani Ronchi, A. Tetrahedron
1972, 28, 3009.
(28) Conan, A.; Sibille, S.; Périchon, J. J. Org. Chem. 1991, 56,
2018.
(29) Fleisher, R.; Galle, D.; Braun, M. Liebigs Ann. Recl. 1997,
1189.
(30) Inoue, Y.; Yamasaki, N.; Shimoyama, H.; Tai, A. J. Org.
Chem. 1993, 58, 1785.
(31) Murray, R. W.; Singh, M.; Jeyaraman, R. J. Am. Chem. Soc.
1992, 114, 1346.
(32) Bulman Page, P. C.; Rassias, G. A.; Bethell, D.; Schilling,
M. B. J. Org. Chem. 1998, 63, 2774.
(33) Dansette, P. M.; Ziffer, H.; Jerina, D. M. Tetrahedron 1976,
32, 2071.
(34) Zanardi, J.; Leriverend, C.; Aubert, D.; Julienne, K.; Metzer,
P. J. Org. Chem. 2001, 66, 5620.
(35) Fetizon, M.; Henry, Y.; Aranda, G.; Audier, H. E.; De Luzes,
H. Org. Mass. Spectrom. 1974, 8, 201.
(36) Majima, T.; Tojo, S.; Ishida, A.; Takamuku, S. J. Org.
Chem. 1996, 61, 7793.
(16) Kessar, S. V.; Singh, P.; Kaur, N. P.; Chawla, U.; Shulka, K.;
Aggarwal, P.; Venugopal, D. J. Org. Chem. 1991, 56, 3908.
(17) Delmond, B.; Pommier, J. C.; Valade, J. J. Organomet.
Chem. 1972, 35, 91.
(18) Tamura, Y.; Bayomi, S. M.; Sumoto, K.; Ikeda, M. Synthesis
1977, 693.
(37) Solladié-Cavallo, A.; Diep-Vohuule, A.; Sunjic, V.;
Vinkovic, V. Tetrahedron: Asymmetry 1996, 7, 1783.
(38) Solladié-Cavallo, A.; Lupattelli, P.; Marsol, C.; Isarno, T.;
Bonini, C.; Caruso, L.; Maiorella, A. Eur. J. Org. Chem.
2002, 1439.
Synthesis 2004, No. 3, 389–400 © Thieme Stuttgart · New York