Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III) Oxidants

Article abstract of DOI:10.1002/ejoc.201800306

Dirhodium(II) complexes and iodine(III) oxidants have found useful applications in synthetic nitrene chemistry. In this study, the combination of the dirhodium(II) complex Rh₂(tpa)₄ (tpa = triphenylacetate) with the iodine(III) oxidant PhI(OPiv)₂ is shown to promote the epoxidation of alkenes in the presence of 2 equivalents of water. The reaction can be applied to diversely substituted alkenes and the corresponding epoxides are isolated with yields of up to 90 %. A possible mechanism involves the dirhodium(II) complex as a Lewis acid species that would tune the oxidizing character of the iodine(III) reagent.

Full text of DOI:10.1002/ejoc.201800306

https://doi.org/10.1002/ejoc.201800306
Full Paper
Alkene Epoxidation
Dirhodium(II)-Mediated Alkene Epoxidation with Iodine(III)
Oxidants
Ali Nasrallah,[a] Gwendal Grelier,[a] Maria Ivana Lapuh,[a,b] Fernando J. Duran,[b]
Benjamin Darses,[a] and Philippe Dauban*[a]
To the memory of Pierre Potier
Abstract: Dirhodium(II) complexes and iodine(III) oxidants applied to diversely substituted alkenes and the corresponding
have found useful applications in synthetic nitrene chemistry. epoxides are isolated with yields of up to 90 %. A possible
In this study, the combination of the dirhodium(II) complex mechanism involves the dirhodium(II) complex as a Lewis acid
Rh2(tpa)4 (tpa = triphenylacetate) with the iodine(III) oxidant species that would tune the oxidizing character of the iodine(III)
PhI(OPiv)2 is shown to promote the epoxidation of alkenes in reagent.
the presence of 2 equivalents of water. The reaction can be
Introduction
to develop a dirhodium(II)-catalyzed alkene epoxidation under
oxygen in the presence of isobutyraldehyde.[9]
Hypervalent iodine compounds are useful reagents in organic
synthesis that allow for performing different types of oxidation
reactions under mild conditions.[1,2] Among the functional
groups likely to react with iodine(III) oxidants, alkenes are valu-
able platforms that give generally access to a wide range of
difunctionalized products.[3] Epoxides, however, can also be ob-
tained by the reaction of iodosylbenzene (PhI=O) with electron-
deficient olefins such as enones and ketenes.[4] Similarly, FeIII-,
MnIII-, CrIII-, RuII- or RuIII complexes inspired by the natural oxy-
genases, can react with PhI=O to generate metal-oxo species
that are highly efficient agents for the epoxidation of simple
alkenes.[1,5]
The combination of the hypervalent iodine chemistry with
the dirhodium(II) catalysis has been translated by several
achievements in synthetic carbene[10] and nitrene[11] chemistry.
Of particular relevance is the ability of dirhodium complexes to
react with an iminoiodinane to afford a metallanitrene species.
The latter allows for functionalizing different types of C(sp3)–H
bond and alkenes,[12] thereby making the dirhodium(II)-cata-
lyzed oxidative amination reactions new efficient tools for the
synthesis of nitrogen-containing natural products and bioactive
compounds (Scheme 1a).[13]
Use of dirhodium(II) paddlewheel complexes for the decom-
position of diazo compounds has led to significant break-
throughs in synthetic carbene chemistry.[6] By comparison, their
ability to mediate selective oxidation reactions has been less
explored although this reactivity was first unveiled in 1982.[7]
Recent studies, nevertheless, have described efficient allylic and
benzylic oxidations resulting from the reaction of a di-
rhodium(II) complex with an oxidant such as tert-butylhydro-
peroxide.[8] Dirhodium caprolactame, particularly, has proved
highly active to mediate these reactions that proceed through
a radical pathway. The mechanistic investigations, then, has led
[a] Institut de Chimie des Substances Naturelles, CNRS UPR 2301,
Univ. Paris-Sud, Université Paris-Saclay,
1, av. de la Terrasse, 91198 Gif-sur-Yvette, France
E-mail: philippe.dauban@cnrs.fr
http://www.icsn.cnrs-gif.fr/spip.php?article666
[b] Departamento de Quimica Organica and UMYMFOR (CONICET-UBA),
Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires,
Buenos Aires, Argentina
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201800306.
Scheme 1. Background for the study.
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Recent investigations in our group, however, have revealed proving the conversion, the epoxide 2a being obtained with a
a different reactivity following the mixing of a dirhodium(II) yield of 72 % (entry 2).
complex and an iodine(III) oxidant. Application of reaction con-
ditions likely to promote nitrene transfers to alkenes, thus, led
us to isolate an epoxide instead of the expected aziridine
(Scheme 1b). This unusual result convinced us to study further
this transformation akin to a dirhodium(II)-assisted alkene ep-
oxidation involving a trivalent iodine reagent. We, therefore,
wish to report in this manuscript the results of our investiga-
tions.
The same observation was made with trifluoroethanol and
the study performed with this solvent and 2 equivalents of H2O
led to an optimized yield of 83 % (entries 3–5). Screening of the
dirhodium(II) complexes again brings to light the highest activ-
ity of Rh2(tpa)4 to mediate the epoxidation reaction (entries 6–
9), a yield of 81 % being obtained using only 0.5 mol-% of this
complex (entries 10 and 11). Finally, reducing the quantity of
the iodine(III) oxidant to 1.2 equivalents does not modify the
yield, as does the replacement of PhI(OPiv)2 by PhI(OAc)2 (en-
tries 12 and 13). We have thus decided to choose the conditions
displayed in entry 12 to explore the scope of the reaction.[16]
We first studied the case of tri-substituted alkenes
(Table 2).[17] Various geranyl and neryl derivatives proved to
react efficiently to afford selectively the corresponding mono-
epoxides 2a–d, with yields between 71 and 81 %.[18] The selec-
tivity probably arises from the inductive effect of the terminal
carboxylate or imide that decreases the reactivity of the proxi-
mal alkene. The epoxide 2e derived from linalyl acetate, on the
other hand, highlights the higher reactivity of a tri-substituted
olefin in the presence of a mono-substituted alkene. Similarly,
epoxides 2f and 2g demonstrates that α,ꢀ-unsaturated ester
and ketone do not react under these conditions.[19] Substrates
1h and 1i, which display a potentially oxidizable benzylic posi-
tion, only led to the epoxides 2h and 2i. Compound 2j shows
the tolerance of the reaction towards the presence of a silyl-
Results and Discussion
In the course of our studies devoted to the search for new
efficient oxidative amination processes, we have found that the
reaction of geranyl acetate 1a with a sulfamate and PhI(OPiv)2
(OPiv = OCOtBu) in the presence of the Rh2(esp)2 complex
(esp = α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid)[14] af-
fords a single product for which the NMR spectroscopic data
clearly indicate the absence of the SO3R motif. Careful analysis
of the NMR and MS spectra, thus, revealed that the isolated
compound was the terminal tri-substituted epoxide 2a.[15] The
formation of such an oxygenated product under the classical
conditions for nitrene addition was puzzling and led us to ex-
plore further the reaction.
A first rapid screening of the reaction parameters in the ab-
sence of the nitrene precursor has shown that the best yields
are obtained with the Rh2(tpa)4 complex (tpa = triphenyl-
acetate) as the catalyst in dichloromethane or trifluoroethanol
(see Table S1 in the Supporting Information). However, we have
rapidly observed that the results strongly depend on the quality
of the solvents with the presence of water being crucial for the
course of the epoxidation reaction. Thus, whereas use of freshly
distilled dichloromethane only leads to traces of 2a (entry 1,
Table 1), the addition of 2 equivalents of water allows for im-
Table 2. Dirhodium(II)-mediated epoxidation of tri-substituted alkenes.[a]
Table 1. Optimization studies for the dirhodium(II)-mediated epoxidation.
Entry
Equiv. H2O Catalyst [mol-%]
Solvent
Yield [%][a]
1
2
3
4
5
6
7
8
0
2
2
1
4
2
2
2
2
2
2
2
2
Rh2(tpa)4 (2)
Rh2(tpa)4 (2)
Rh2(tpa)4 (2)
Rh2(tpa)4 (2)
Rh2(tpa)4 (2)
Rh2(OCOC3F7)4 (2)
DCM
DCM
<5
72
83
52
83
40
50
<10
60
81
40
81
78
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
trifluoroethanol
Rh2(OCOC7H15)4 (2)
Rh2(OAc)4 (2)
Rh2(esp)2 (2)
Rh2(tpa)4 (0.5)
Rh2(tpa)4 (0.1)
Rh2(tpa)4 (0.5)
Rh2(tpa)4 (0.5)
9
10
11
12[b]
13[c]
[a] Isolated yields. [b] The reaction was performed with 1.2 equiv. of
PhI(OPiv)2. [c] With 1.2 equiv. of PhI(OAc)2.
[a] Isolated yields. [b] 3 h of reaction.
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protecting group. Finally, spiro derivatives 2k and 2l can also fully degassed trifluoroethanol affords the epoxide 2i with a
be obtained from cyclic alkylidene starting materials.
similar yield, whereas the reaction of geranyl acetate in the
presence of the radical inhibitor BHT allowed us for obtaining
2a without a noticeable change in the conversion. The hypoth-
esis of a radical pathway was thus ruled out based on these
observations.
The reaction also applies to di-substituted olefins (Table 3).
Trans-epoxides were generally isolated from the corresponding
1
(E)-alkenes, except in the case of 2n for which H NMR shows
the formation of a small amount of the cis-epoxide. In a similar
manner, the (Z)-olefin 1p leads to slight isomerization under
The formation of metal-oxo species as those reported with
the reaction conditions, the corresponding epoxide 2p being Fe, Mn, Cr or Ru complexes,[5] is unknown with dirhodium(II)
isolated as a 13:1 mixture of cis:trans isomers. Gem-di-substi- complexes to the best of our knowledge. We, therefore, pro-
tuted alkenes are also relevant substrates for the reaction as pose that the latter might act as a Lewis acid species in the
demonstrated by compound 2q.
alkene epoxidation according to the mechanism depicted in
Scheme 3.[22–24]
Table 3. Dirhodium(II)-mediated epoxidation of di-substituted alkenes.[a]
[a] Isolated yields. [b] 4 h of reaction. Isolated as a 10:1 mixture of trans:cis
isomers. [c] Isolated as a 13:1 mixture of cis:trans isomers according to the
1H NMR spectroscopy.
Scheme 3. Mechanism for the dirhodium-mediated epoxidation of alkene.
Finally, whereas simple terminal olefins such as a protected
but-3-en-1-ol do not react, aromatic alkenes can be converted
to epoxides. Styrene derivatives substituted by a cyano or an
ester function, thus, afford the corresponding epoxides in good
yields (Scheme 2).[20] However, the reaction with styrene as well
as with α- or ꢀ-substituted derivatives led to the formation of
an intractable mixture of products probably resulting from the
oxidative cleavage of the epoxide.[21]
The presence of water could induce a first ligand exchange
with the PhI(OPiv)2 reagent to afford the iodine(III) species A.
Then, by analogy with the acknowledged mechanism of
rhodium-catalyzed nitrene transfer with iminoiodinanes,[12] we
suggest that the dirhodium(II) complex react with A to afford
the intermediate of type B. The latter could react with a double
bond to produce the cyclic iodonium C[25] that could undergo
sequential nucleophilic displacement with water to give the ep-
oxide 2, and release iodobenzene and water as by-products
while regenerating the dirhodium(II) complex. This mechanistic
hypothesis is in line with the lack of reactivity observed with
poorly nucleophilic alkenes such as mono-substituted terminal
olefins that could not add to the iodonium B. On the other
hand, the isomerization observed in the case of compounds
2n and 2p could be rationalized by a hypothetical equilibrium
between the intermediate C and the carbocationic species D
that has been invoked in our previous study on alkene difunc-
tionalization with rhodium-bound nitrenes.[12m]
Scheme 2. Dirhodium(II)-mediated epoxidation of styrene derivatives.
Several test experiments have been made to investigate the
possible mechanism for this transformation. First, the reaction
performed from geranyl acetate in the absence of the di-
rhodium(II) complex only led to traces of the corresponding
epoxide 2a, thereby demonstrating its key role in the process.
Conclusions
The extensive mechanistic studies on the rhodium-catalyzed This manuscript has documented an unusual reactivity arising
aerobic Mukaiyama epoxidation performed by Doyle, then, led from the combination of dirhodium(II) catalysts and iodine(III)
us to consider the possible involvement of radicals.[9] The reac- oxidants. In the presence of a stoichiometric amount of an alk-
tion of 2-methyl-5-phenylpent-2-ene 1i carried out with care- ene and two equivalents of water, the reaction gives rise to
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(35.2 mg, 79 %). The 1H NMR spectrum is in accordance with the
literature. 1H NMR (300 MHz, CDCl3): δ = 5.41 (t, J = 7.1 Hz, 1 H),
4.59 (d, J = 7.1 Hz, 2 H), 2.71 (t, J = 6.2 Hz, 1 H), 2.32–2.20 (m, 2 H),
2.05 (s, 3 H), 1.79 (s, 3 H), 1.73–1.54 (m, 2 H), 1.31 (s, 3 H), 1.27 (s, 3
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 171.2, 141.8, 119.9, 73.9,
61.0, 58.5, 29.0, 27.7, 25.0, 23.6, 21.2, 18.8 ppm.
epoxides that have been isolated with yields in the 60–90 %
range. Accordingly, this method could provide an alternative to
classical methods for epoxidation involving, for example, the
use of m-CPBA. The transformation applies to tri-, di-, and
mono-substituted alkenes that display a nucleophilic character.
Since this unusual reactivity was initially noticed under condi-
tions for catalytic nitrene additions, it should be considered as
a possible side reaction in further studies centered on allylic
amination or alkene aziridination.
5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-1-en-3-yl Acetate
(2e):[9] Prepared according to the general procedure for epoxidation
using 1e (39.2 mg, 200 μmol) as the starting material. After purifica-
tion by flash chromatography on silica gel (9:1 petroleum ether/
1
AcOEt), 2e was obtained as a colorless oil (38.0 mg, 90 %). The H
NMR spectrum is in accordance with the literature. 1H NMR
(300 MHz, CDCl3): δ = 6.04–5.88 (m, 1 H), 5.25–5.07 (m, 2 H), 2.71
(t, J = 6.2 Hz, 1 H), 2.01 (s, 3 H), 1.95–1.85 (m, 2 H), 1.55 (d, J =
6.9 Hz, 3 H), 1.68–1.40 (m, 2 H), 1.31 (s, 3 H), 1.25 (d, J = 5.3 Hz, 3
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 170.0, 141.6, 141.4, 113.7,
113.6, 82.6, 82.5, 64.1, 58.5, 36.4, 25.0, 23.8, 23.7, 23.6, 22.3,
18.7 ppm.
Experimental Section
General Procedure for the Epoxidation Reaction: A flask contain-
ing the substrate (200 μmol, 1.00 equiv.) was charged with Rh2(tpa)4
(1.40 mg, 1.00 μmol, 0.5 mol-%) and 1.30 mL of 2,2,2-trifluoro-
ethanol. To this mixture were added PhI(OPiv)2 (97.5 mg, 240 μmol,
1.20 equiv.) in one portion, and, then, H2O (7.20 μL, 400 μmol,
2.00 equiv.). The mixture was stirred between 4 and 16 h at room
temperature. After concentration under reduced pressure, the resi-
due was purified by flash chromatography on silica gel.
(3,3-Dimethyloxiran-2-yl)methyl Cinnamate (2f): Prepared ac-
cording to the general procedure for epoxidation using 1f (43.2 mg,
200 μmol) as the starting material. After purification by flash chro-
matography on silica gel (9:1 petroleum ether/AcOEt) 2f was ob-
tained as a colorless liquid (27.6 mg, 60 %). 1H NMR (300 MHz,
CDCl3): δ = 7.77–7.70 (m, 1 H), 7.55–7.51 (m, 2 H), 7.41–7.38 (m, 3
H), 6.48 (d, J = 16.1 Hz, 1 H), 4.49 (dd, J = 12.1, 4.2 Hz, 1 H), 4.15
(dd, J = 12.1, 6.8 Hz, 1 H), 3.11–3.05 (m, 1 H), 1.38 (s, 3 H), 1.37 (s,
3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 166.9, 145.6, 134.4, 130.5,
129.0 (2 C), 128.3 (2 C), 117.6, 63.6, 60.7, 58.2, 24.7, 19.1 ppm. IR
(E)-5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-2-en-1-yl Acetate
(2a):[26] Prepared according to the general procedure for epoxid-
ation using 1a (39.2 mg, 200 μmol) as the starting material. After
purification by flash chromatography on silica gel (9:1 petroleum
ether/AcOEt), 2a was obtained as a colorless oil (35.2 mg, 81 %).
1
1
The H NMR spectrum is in accordance with the literature. H NMR
(500 MHz, CDCl3): δ = 5.39 (t, J = 6.8 Hz, 1 H), 4.59 (d, J = 6.8 Hz, 2
H), 2.70 (t, J = 6.0 Hz, 1 H), 2.30–2.10 (m, 2 H), 2.05 (s, 3 H), 1.73 (s,
3 H), 1.70–1.63 (m, 2 H), 1.31 (s, 3 H), 1.26 (s, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 171.2, 141.4, 119.0, 64.0, 61.3, 58.5, 36.3, 27.1,
24.9, 21.1, 18.8, 16.5 ppm.
(neat): ν = 2962, 2928, 1712, 1635, 1526, 1451, 1351, 1307, 1254,
˜
1165, 1133 cm–1. HRMS = [M + H]+ calculated for [C14H17O3]+
233.1172, found 233.1176.
=
(R)-2-Methyl-5-[(R)-2-methyloxiran-2-yl]cyclohex-2-en-1-one
(2g):[30] Prepared according to the general procedure for epoxid-
ation using (R)-Carvone (30.0 mg, 200 μmol) as the starting material.
After purification by flash chromatography on silica gel (9:1 petro-
leum ether/AcOEt), 5 was obtained as a yellow oil (24.1 mg, 73 %).
(E)-5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-2-en-1-yl 3,5-Di-
nitro-benzoate (2b):[27] Prepared according to the general proce-
dure for epoxidation using 1b (69.0 mg, 200 μmol) as the starting
material. After purification by flash chromatography on silica gel
(9:1 petroleum ether/AcOEt), 2b was obtained as a yellow solid
(55.0 mg, 76 %). The 1H NMR spectrum is in accordance with the
literature. 1H NMR (500 MHz, CDCl3): δ = 9.22 (t, J = 2.1 Hz, 1 H),
9.16 (d, J = 2.1 Hz, 2 H), 5.57–5.52 (m, 1 H), 4.98 (d, J = 7.3 Hz, 2 H),
2.72 (dd, J = 6.9, 5.5 Hz, 1 H), 2.34–2.19 (m, 2 H), 1.84 (s, 3 H), 1.77–
1.64 (m, 2 H), 1.31 (s, 3 H), 1.28 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 162.7, 148.8 (2 C), 143.7, 134.3, 129.6 (2 C), 122.4, 117.8,
63.9, 63.7, 58.5, 36.5, 27.2, 25.0, 18.9, 16.8 ppm.
1
1
The H NMR spectrum is in accordance with the literature. H NMR
(300 MHz, CDCl3): δ = 6.74 (s, 1 H), 2.69 (dd, J = 11.0, 4.5 Hz, 1 H),
2.63–2.57 (m, 2 H), 2.50–2.33 (m, 2 H), 2.33–2.14 (m, 2 H), 1.78 (s, 3
H), 1.32 (d, J = 5.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
199.0, 144.3, 144.0, 135.7, 58.1, 58.0, 53.1, 52.5, 41.5, 40.8, 40.5, 40.1,
28.0, 27.8, 19.2, 18.5, 15.8 ppm.
2,2-Dimethyl-3-(3-phenylpropyl)oxirane (2h): Prepared accord-
ing to the general procedure for epoxidation using 1h (35.0 mg,
200 μmol) as the starting material. After purification by flash chro-
matography on silica gel (9.5:0.5 petroleum ether/AcOEt), 2h was
obtained as a colorless liquid (26.0 mg, 70 %). 1H NMR (300 MHz,
CDCl3): δ = 7.30–7.25 (m, 3 H), 7.19 (d, J = 6.6 Hz, 2 H), 2.74 (dd, J =
11.4, 5.0 Hz, 1 H), 2.70–2.63 (m, 2 H), 1.93–1.66 (m, 2 H), 1.62–1.52
(m, 2 H), 1.30 (s, 3 H), 1.24 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 142.2, 128.5 (2 C), 128.4 (2 C), 125.9, 64.4, 58.31 35.8, 28.6, 28.5,
(E)-2-[5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-2-en-1-yl]iso-
indoline-1,3-dione (2c):[28] Prepared according to the general pro-
cedure for epoxidation using 1c (57.0 mg, 200 μmol) as the starting
material. After purification by flash chromatography on silica gel
(9:1 petroleum ether/AcOEt), 2c was obtained as a white powder
(42.0 mg, 70 %). The 1H NMR spectrum is in accordance with the
literature. 1H NMR (300 MHz, CDCl3): δ = 7.88–7.80 (m, 2 H), 7.70
(dd, J = 4.9, 3.2 Hz, 2 H), 5.31 (t, J = 7.0 Hz, 1 H), 4.29 (d, J = 7.0 Hz,
2 H), 2.67 (t, J = 6.2 Hz, 1 H), 2.26–2.05 (m, 2 H), 1.85 (s, 3 H), 1.69–
1.57 (m, 2 H), 1.26 (s, 3 H), 1.24 (s, 3 H) ppm. 13C NMR (75 MHz,
CDCl3): δ = 168.2 (2 C), 139.9, 134.0 (2 C), 132.4 (2 C), 123.3 (2 C),
118.8, 64.0, 58.5, 36.3, 35.9, 27.2, 24.9, 18.8, 16.5 ppm.
25.0, 18.8 ppm. IR (neat): ν = 2959, 2921, 2860, 1496, 1455, 1376,
˜
1283, 1249, 1153, 1114, 890, 745, 697 cm–1. HRMS = [M + H]+ calcu-
lated for [C13H19O]+ = 191.1430, found 191.1442.
2,2-Dimethyl-3-phenethyloxirane (2i):[31] Prepared according to
the general procedure for epoxidation using 1i (32.0 mg, 200 μmol)
as the starting material. After purification by flash chromatography
(Z)-5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-2-en-1-yl Acetate
(2d):[29] Prepared according to the general procedure for epoxid- on silica gel (9:1 petroleum ether/AcOEt), 2i was obtained as a white
1
ation using nerol acetate (39.2 mg, 200 μmol) as the starting mate- solid (25.0 mg, 72 %). The H NMR spectrum is in accordance with
1
rial. After purification by flash chromatography on silica gel (9:1
petroleum ether/AcOEt), 2d was obtained as a colorless oil
the literature. H NMR (300 MHz, CDCl3): δ = 7.28 (m, 3 H), 7.20 (d,
J = 6.0 Hz, 2 H), 2.92–2.64 (m, 3 H), 1.99–1.73 (m, 2 H), 1.27 (s, 3 H),
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1.12 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 141.6, 128.6 (2 C),
128.5 (2 C), 126.2, 64.0, 58.7, 32.9, 30.9, 24.9, 18.7 ppm.
(3R*,4R*)-tert-Butyl[2-(3-ethyloxiran-2-yl)ethoxy]dimethylsilane
(2o):[34] Prepared according to the general procedure for epoxid-
ation using 1o (42.9 mg, 200 μmol) as the starting material. After
purification by flash chromatography on silica gel (9:1 petroleum
ether/AcOEt), 2o was obtained as a white powder (32.7 mg, 71 %).
The H NMR spectrum is in accordance with the literature. H NMR
(300 MHz, CDCl3): δ = 3.75 (dd, J = 6.3, 6.0 Hz, 2 H), 2.81 (td, J =
6.0, 2.4 Hz, 1 H), 2.69 (td, J = 5.4, 2.4 Hz, 1 H), 1.82–1.63 (dt, J =
12.9, 6.6 Hz, 2 H), 1.57 (m, 2 H), 1.07 (t, J = 7.5 Hz, 3 H), 0.92 (s, 9
H), 0.09 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 60.2 (2 C), 56.2,
35.7, 26.0 (3 C), 25.3, 18.4, 10.0, –5.2 (2 C) ppm.
tert-Butyl[(3,3-dimethyloxiran-2-yl)methoxy]dimethylsilane
(2j):[32] Prepared according to the general procedure for epoxid-
ation using 1j (40.0 mg, 200 μmol) as the starting material. After
purification by flash chromatography on silica gel (9.5:0.5 petroleum
ether/AcOEt), 2j was obtained as a colorless oil (32.4 mg, 75 %).
1
1
1
1
The H NMR spectrum is in accordance with the literature. H NMR
(300 MHz, CDCl3): δ = 3.74 (d, J = 5.3 Hz, 2 H), 2.90 (t, J = 5.3 Hz, 1
H), 1.34 (s, 3 H), 1.28 (s, 3 H), 0.91 (s, 9 H), 0.09 (s, 3 H), 0.08 (s, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 64.2, 62.5, 58.3, 26.0 (3 C), 25.0
(2 C), 19.0, –5.0, –5.2 ppm.
(3R*,4S*)-tert-Butyl[2-(3-ethyloxiran-2-yl)ethoxy]dimethylsilane
(2p):[35] Prepared according to the general procedure for epoxid-
ation using 1p (42.9 mg, 200 μmol) as the starting material. After
purification by flash chromatography on silica gel (9:1 petroleum
ether/AcOEt), 2p was obtained as a mixture of 13:1 cis:trans isomers,
and as a colorless liquid (32.7 mg, 71 %). Only the major diastereo-
isomer is described for clarity. The 1H NMR spectrum is in accord-
ance with the literature. 1H NMR (500 MHz, CDCl3): δ = 3.81–3.77
(m, 2 H), 3.09–3.04 (m, 1 H), 2.93–2.88 (m, 1 H), 1.84–1.74 (m, 1 H),
1.72–1.63 (m, 1 H), 1.61–1.47 (m, 2 H), 1.05 (t, J = 7.5 Hz, 3 H), 0.90
(s, 9 H), 0.07 (s, 6 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 60.7, 58.4,
54.9, 31.3, 26.0 (3 C), 21.4, 18.5, 10.7, –5.2 (2 C) ppm.
Ethyl 3-(1-Oxaspiro[2.5]octan-2-yl)propanoate (2k): Prepared ac-
cording to the general procedure for epoxidation using 1k (39.3 mg,
200 μmol) as the starting material. After purification by flash chro-
matography on silica gel (9:1 petroleum ether/AcOEt), 2k was ob-
1
tained as a colorless oil (30.0 mg, 71 %). H NMR (300 MHz, CDCl3):
δ = 4.15 (q, J = 7.1 Hz, 2 H), 2.80–2.72 (m, 1 H), 2.48 (dd, J = 11.8,
7.6 Hz, 2 H), 2.00–1.63 (m, 4 H), 1.62–1.47 (m, 8 H), 1.26 (t, J = 7.0 Hz,
3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 173.6, 60.5, 51.3, 43.1, 32.2,
31.7, 29.5, 28.7, 27.4, 24.4 (1 C, 1 C), 14.4 ppm. IR (neat): ν = 2928,
˜
2860, 1736, 1690, 1455, 1375, 1275, 1169, 1123, 1031, 934 cm–1
.
HRMS = [M + H]+ calculated for [C12H21O3]+ = 213.1485, found
213.1471.
2-(2-Methyloxiran-2-yl)ethyl Benzoate (2q):[36] Prepared accord-
ing to the general procedure for epoxidation using 1q (32.4 mg,
200 μmol) as the starting material. After purification by flash chro-
matography on silica gel (9.5:0.5 petroleum ether/AcOEt), 2q was
obtained as a brown powder (25.0 mg, 71 %). The 1H NMR spectrum
Ethyl 2-Phenethyl-1-oxa-6-azaspiro[2.5]octane-6-carboxylate
(2l): Prepared according to the general procedure for epoxidation
using 1l (55.0 mg, 200 μmol) as the starting material. After purifica-
tion by flash chromatography on silica gel (9:1 petroleum ether/
1
1
AcOEt), 2l was obtained as a colorless oil (38.0 mg, 67 %). H NMR
is in accordance with the literature. H NMR (300 MHz, CDCl3): δ =
(300 MHz, CDCl3): δ = 7.34–7.25 (m, 2 H), 7.24–7.16 (m, 3 H), 4.14
(q, J = 6.4 Hz, 2 H), 3.82–3.62 (m, 2 H), 3.44–3.26 (m, 2 H), 2.88–2.82
(m, 2 H), 2.80–2.65 (m, 1 H), 2.02–1.67 (m, 4 H), 1.52–1.31 (m, 2 H),
1.26 (t, J = 6.4 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 155.6,
141.2, 128.7 (2 C), 128.6 (2 C), 126.4, 63.9, 61.5, 61.1, 42.2, 42.3, 34.6,
8.04 (d, J = 7.8 Hz, 2 H), 7.57 (t, J = 7.1 Hz, 1 H), 7.45 (t, J = 7.7 Hz,
2 H), 4.54–4.36 (m, 2 H), 2.72 (d, J = 4.7 Hz, 1 H), 2.64 (d, J = 4.7 Hz,
1 H), 2.18–1.94 (m, 2 H), 1.42 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 166.7, 133.2, 129.7 (2 C), 129.4, 128.6 (2 C), 74.4, 61.6, 59.9, 35.9,
21.5 ppm.
32.8, 30.0, 29.0, 14.8 ppm. IR (neat): ν = 2962, 2931, 2863, 1693,
˜
4-(Oxiran-2-yl)benzonitrile (2r):[37] Prepared according to the gen-
eral procedure for epoxidation using 1r (28.8 mg, 200 μmol) as the
starting material. After purification by flash chromatography on sil-
ica gel (9.5:0.5 petroleum ether/AcOEt), 2r was obtained as a white
powder (24.5 mg, 85 %). The 1H NMR spectrum is in accordance
with the literature. 1H NMR (300 MHz, CDCl3): δ = 7.64 (d, J = 7.8 Hz,
2 H), 7.39 (d, J = 7.8 Hz, 2 H), 3.91 (dd, J = 2.5, 4.0 Hz, 1 H), 3.21
(dd, J = 5.4, 4.2 Hz, 1 H), 2.76 (dd, J = 5.5, 2.4 Hz, 1 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 144.0, 132.5 (2 C), 126.3 (2 C), 118.7,
112.1, 51.7 (2 C) ppm.
1428, 1378, 1275, 1229, 1169, 1125, 1093, 1069, 1026, 890, 764, 749,
698 cm–1. HRMS = [M + H]+ calculated for [C17H24NO3]+ = 290.1750,
found 290.1780.
4-Nitrobenzyl 2-(3-Methyloxiran-2-yl)acetate (2m): Prepared ac-
cording to the general procedure for epoxidation using 1m
(47.0 mg, 200 μmol) as the starting material. After purification by
flash chromatography on silica gel (9:1 petroleum ether/AcOEt), 2m
1
was obtained as a colorless oil (35.5 mg, 71 %). H NMR (500 MHz,
CDCl3): δ = 8.23 (d, J = 8.3 Hz, 2 H), 7.53 (d, J = 8.3 Hz, 2 H), 5.26
(s, 2 H), 3.05 (d, J = 4.4 Hz, 1 H), 2.89–2.82 (m, 1 H), 2.65 (ddd, J =
22.9, 16.4, 5.6 Hz, 2 H), 1.34 (d, J = 5.0 Hz, 3 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 170.2, 143.0, 128.5 (2 C), 124.0 (2 C), 65.2, 54.8,
2-(Oxiran-2-yl)benzonitrile (2s):[37] Prepared according to the gen-
eral procedure for epoxidation using 1s (26.0 mg, 200 μmol) as the
starting material. After purification by flash chromatography on sil-
ica gel (9:1 petroleum ether/AcOEt), 2s was obtained as a white
powder (23.0 mg, 80 %). The 1H NMR spectrum is in accordance
with the literature. 1H NMR (300 MHz, CDCl3): δ = 7.66 (d, J = 7.6 Hz,
1 H), 7.60 (t, J = 7.6 Hz, 1 H), 7.40 (t, J = 7.6 Hz, 1 H), 7.34 (d, J =
7.6 Hz, 1 H), 4.25 (s, 1 H), 3.29–3.24 (m, 1 H), 2.78–2.73 (m, 1 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 133.5 (2 C), 132.9 (2 C), 128.6,
125.0, 101.8, 51.6, 50.5 ppm.
54.6, 37.7, 17.4 ppm. IR (neat): ν = 2959, 2921, 2860, 1550, 1475,
˜
1455, 1376, 1283, 1249, 1153, 1114, 890, 745 cm–1. HRMS = [M +
H]+ calculated for [C12H14NO5]+ = 252.0876, found 252.0866.
(E)-3-(3-Methyloxiran-2-yl)allyl Acetate (2n):[33] Prepared accord-
ing to the general procedure for epoxidation using trans,trans-2,4-
hexadienyl acetate (28.0 mg, 200 μmol) as the starting material.
After purification by flash chromatography on silica gel (9.5:0.5 pe-
troleum ether/AcOEt), 2n was obtained as a mixture of 10:1 trans:cis
isomers, and as a colorless oil (22.5 mg, 72 %). Only the major dia- Methyl 4-(oxiran-2-yl)benzoate (2t):[38] Prepared according to the
stereoisomer is described for clarity. The 1H NMR spectrum is in
accordance with the literature. 1H NMR (300 MHz, CDCl3): δ = 6.07–
5.90 (m, 1 H), 5.51 (dd, J = 15.4, 7.9 Hz, 1 H), 4.58 (d, J = 5.9 Hz, 2
H), 3.11 (dd, J = 14.9, 7.2 Hz, 1 H), 2.92 (d, J = 5.1 Hz, 1 H), 2.08 (s,
3 H), 1.35 (d, J = 5.1 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
171.6, 132.0, 128.8, 64.0, 58.6, 56.7, 21.0, 17.6 ppm.
general procedure for epoxidation using 1t (32.4 mg, 200 μmol) as
the starting material. After purification by flash chromatography on
silica gel (9:1 petroleum ether/AcOEt), 2t was obtained as a white
powder (27.0 mg, 76 %). The 1H NMR spectrum is in accordance
with the literature. 1H NMR (300 MHz, CDCl3): δ = 8.05 (d, J = 7.7 Hz,
1 H), 7.38 (d, J = 7.7 Hz, 1 H), 3.95 (s, 4 H), 3.25–3.19 (m, 1 H), 2.87–
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2.79 (m, 1 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 166.9, 143.0, 130.0
(2 C), 126.9, 125.6 (2 C), 52.3, 52.0, 51.6 ppm.
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Acknowledgments
We wish to thank the French National Research Agency (pro-
gram number ANR-11-IDEX-0003-02, CHARMMMAT ANR-11-
LABX-0039, and ANR-15-CE29-0014-01; fellowship to A. N.), the
Ministère de l'Enseignement Supérieur et de la Recherche (fel-
lowship to G. G.), the Saint Exupery Program (grant to M. I. H.),
the ECOS-Sud Committee (Action A15E04), and the Institut de
Chimie des Substances Naturelles for their support.
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1983, 105, 6728; b) P. Müller, C. Baud, Y. Jacquier, Tetrahedron 1996, 52,
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Keywords: Hypervalent Iodine · Rhodium · Epoxidation ·
Alkenes · Lewis acids
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Though the difference in yields between the entries 12 and 13 is not
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[17]
[18]
The reaction with a tetrasubstituted alkene only leads to the recovery
of the starting material.
An allylic alcohol such as geraniol does not afford the corresponding
epoxide under the reaction conditions. A complex mixture of products,
instead, is obtained as indicated by the 1H NMR of the crude.
In order to circumvent the lack of reactivity of α,ꢀ-unsaturated ketones,
these were converted to cyclic ketals. However, application of the reac-
tion conditions to the latter only leads to the starting ketone following
cleavage of the ketal.
It is worth mentioning that the reaction of m-CPBA with the ortho-cyano
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[19]
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K. Miyamoto, N. Tada, M. Ochiai, J. Am. Chem. Soc. 2007, 129, 2772.
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Received: February 21, 2018
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Alkene Epoxidation
A. Nasrallah, G. Grelier,
M. I. Lapuh, F. J. Duran, B. Darses,
P. Dauban* ........................................... 1–8
The combination of rhodium(II) cataly- presence of water. The reaction in-
sis and iodine(III) oxidant, which is well volves a Lewis acidic dirhodium(II)
acknowledged for inducing nitrogen complex bound to an iodonium spe-
atom transfer, is shown to promote an cies that would undergo nucleophilic
unusual alkene epoxidation in the displacement with water.
Dirhodium(II)-Mediated Alkene Ep-
oxidation with Iodine(III) Oxidants
https://doi.org/10.1002/ejoc.201800306
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