C?O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non-Rubottom Oxidation

Article abstract of DOI:10.1002/adsc.201900271

Malonyl peroxides act both as oxidants and reagents for C?O coupling in reactions with methyl and silyl enol ethers. In the proposed conditions, the oxidative C?O coupling of malonyl peroxides with enol ethers selectively proceeds, bypassing the traditional Rubottom hydroxylation of enol ethers by peroxides. It was observed that the oxidative [5+2] cycloaddition of malonyl peroxides and enol ethers is the key stage of the discovered process. Oxidative C?O coupling of silyl enol ethers leads to the formation of α-acyloxyketones with a free carboxylic acid group. A specially developed preparative one-pot procedure transforms ketones via silyl enol ethers formation and the following coupling into α-acyloxyketones with yields 35–88%. The acid-catalyzed coupling with methyl enol ethers gives remarkable products while retaining the easily oxidizable enol fragment. Furthermore, these molecules contain a free carboxylic acid group, thus these nontrivial products contain two usually incompatible acid and enol ether groups. (Figure presented.).

Full text of DOI:10.1002/adsc.201900271

Title: C-O coupling of malonyl peroxides with enol ethers via [5+2]
cycloaddition: non-Rubottom oxidation
Authors: Vera Vil', Evgenii Sergeevich Gorlov, Oleg Vadimovich
Bityukov, Yana Arthurovna Barsegyan, Yulia Evgenievna
Romanova, Valentina Merkulova, and Alexander Terent'ev
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900271
Link to VoR: http://dx.doi.org/10.1002/adsc.201900271

Advanced Synthesis & Catalysis
10.1002/adsc.201900271
Very Important Publication
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
C-O coupling of malonyl peroxides with enol ethers via [5+2]
cycloaddition: non-Rubottom oxidation
a
a,b
a
a
Vera A. Vil’ , Evgenii S. Gorlov , Oleg V. Bityukov , Yana A. Barsegyan , Yulia E.
a,b
a
a,b
Romanova , Valentina M. Merkulova and Alexander O. Terent’ev *
a
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991,
Russian Federation. E-mail: alterex@yandex.ru, terentev@ioc.ac.ru
D. I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow, 125047, Russian
b
Federation.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. Malonyl peroxides act both as oxidants and The acid-catalyzed coupling with methyl enol ethers gives
reagents for C–O coupling in reactions with methyl and silyl remarkable products while retaining the easily oxidizable
enol ethers. In the proposed conditions, the oxidative C-O enol fragment. Furthermore, these molecules contain a free
coupling of malonyl peroxides with enol ethers selectively carboxylic acid group, thus these nontrivial products
proceeds, bypassing the traditional Rubottom hydroxylation contain two usually incompatible acid and enol ether
of enol ethers by peroxides. It was observed that the groups.
oxidative [5+2] cycloaddition of malonyl peroxides and enol
ethers is the key stage of the discovered process. Oxidative Keywords: Oxidation; Cross-coupling; Peroxides;
C-O coupling of silyl enol ethers leads to the formation of α- Ketones; Enols
acyloxyketones with a free carboxylic acid group. A
specially developed preparative one-pot procedure
transforms ketones via silyl enol ethers formation and the
following coupling into α-acyloxyketones with yields 35-
8
8%.
differences determine a wide range of unusual
chemical properties of malonyl peroxides: instead of
oxygenation, an oxygen atom of the malonyl
peroxide links together the two molecules forming a
product. The absence of an acidic proton prevents
acid-catalyzed side processes.
Introduction
The construction of chemical bonds by oxidative
cross-coupling (cross-dehydrogenative coupling) is a
promising and thriving field of modern organic
chemistry. The formation of a new bond occurs with
high atom efficiency and no functional groups are
required.[ Recently we reported efficient methods
The main approaches to oxidation of double bond
[
16]
by oxygen-containing oxidizers
are [2+2]
1]
cycloaddition of singlet oxygen resulted in
[
2]
[17]
[18]
for oxidative C–O coupling of β-dicarbonyl and N-
heterocyclic[ compounds with diacyl peroxides, in
which one of the reagents, diacyl peroxide, acts both
as an O-component and as an oxidizing agent. Cyclic
dioxetanes,
ozonolysis providing ozonides
and
3]
processes including oxidation by oxygen-based
[
19]
[20]
systems,
oxaziridines,
inorganic oxygen-
[
21]
[22]
[23]
containing oxidizers,
peracids,
dioxiranes,
[4]
[24]
diacyl peroxides firstly prepared in the 1950s were
rediscovered a few years ago,[5] when previously
practically unavailable reactions stereoselective syn-
and systems based on ROOH (Scheme 1). In this
study we disclosed power of oxidative [5+2]
cycloaddition of malonyl peroxide and double bond
[
6]
[7]
[6a, 7]
and anti-dihydroxylation
of alkenes, arene
as an alternative strategy to double bond
oxidation,[
8]
10]alkene
oxyamination,
[9]
and
oxidation (Scheme 1).
[
dioxygenation,
Hofmann–Löffler–Freytag-type
The present study reported new oxidative
transformations of enol ethers. Malonyl peroxides
react with enol ethers without transfer of solely active
oxygen and formation of oxygenated products.
Surprisingly, that silyl enol ethers form α-
acyloxyketones with free carboxylic acid group,
while methyl enol ethers yield α'-acyloxyenol ethers
with free carboxylic acid group in acidic conditions.
It should be noted that the starting malonyl peroxides
[
11]
[12]
reaction,
selective sulfide oxidation,
peracids
formation,[
13]
ring
opening/halogenation of
and the [3 + 2] cycloaddition of
[14]
cycloalkanols,
arynes to azides[ were realized. High oxidative
ability, cyclic structure and absence of an acidic
proton attached to the peroxide group favorably differ
malonyl peroxides from related oxidants — peracids
and noncyclic diacyl peroxides. These fundamental
15]
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201900271
are easily synthesized in one step from available
malonic acids or esters using urea hydrogen peroxide
oxygen-atom transfer role, as well as the removal of
oxidant residual and catalysts after the reaction. To
our knowledge α-oxyfunctionalization of ketones
with introduction of more functionally rich fragment
has not previously been accomplished.
[6a, 25]
and methanesulfonic acid with good yields.
The present study advances two aspects of modern
synthetic chemistry: the use of peroxides for the
development of oxidative processes and the selective
oxidative C-O coupling of carbonyl compounds.
Results and Discussion
In the present work we discovered unusual
chemical behavior of the malonyl peroxides with silyl
and alkyl enol ethers. According to Rubottom process,
acyl hydroperoxides (peracids) as a rule react with
silyl enol ethers via [1+2] cycloaddition followed by
rearrangement with formation of α-hydroxy ketones
[65]
(
Scheme 2).
Scheme 1. Diversity of double bond oxidation approaches.
Scheme 2. Rubottom oxidation by acyl hydroperoxides.
The α-oxygenated mono-carbonyl compounds are
structural units in a wide range of natural and
bioactive products[ and useful intermediates for
preparation of a variety of pharmaceutically active
26]
Despite the possibility of the traditional Rubottom
[65-66]
hydroxylation of enol ethers by peroxides,
the
[27]
compounds.
Well-known examples include
oxidative C-O coupling of malonyl peroxides with
enol ethers selectively proceeds instead in the
proposed conditions. Interestingly, the result of
reaction greatly depends on the nature of enol ether –
the interaction of malonyl peroxides 4 with silyl enol
ethers 2 led to α-acyloxylated ketones 5, whereas
reaction of malonyl peroxides 4 with methyl enol
ethers 3 affords α’-acyloxylated methyl enol ethers 6
(Scheme 3). At first glance, it seems impossible to
preserve the enol double bond in the oxidative
process. Two related processes are known. First, the
cortisol,[
28]
prednisolone,
[29]
paeonilactone B,
[30]
[33]
[31]
[32]
doxorubicin, phyllaemblic acid, aryloxindole,
donaxaridine[
34]
and doxycycline.
[35]
Hence, user-
friendly methods for synthesis of α-hydroxy and α-
oxo carbonyl compounds from ketones attract great
attention.
In a number of studies direct hydroxylation of
ketones[ was achieved by using hypervalent iodine
36]
compounds,[
DMSO/I
DMSO/HBr,
nitrobenzenesulfonate,
37]
molecular oxygen,
[38]
I
/O ,
2
[39]
2
2
[40]
2
or DMSO/NBS,
DMSO/CuBr
/ [43]
i
or
p-
and
[41]
thallium(III)
oxidation
of
enol
ethers
by
dimethyl
[
42]
Ti(O Pr)
4
/TBHP
peroxydicarbonate resulted in the introduction of
PhNO/TFA[ . In regard to the oxyfunctionalization
44]
[67]
methylcarbonate group in α-position. Second, the
[45]
of carbonyl targets, they were previously limited to
reaction of lithium enolates and enol ethers with
the alkoxy,[ peroxy, oxygen-sulfonyl, oxygen-
46]
[47]
[48]
dibenzyl
peroxydicarbonate
forms
α-
phosphoryl,[ aminoxy groups. In a few studies α-
49]
[50]
[68]
benzyloxycarbonyl ketones. It should be noted that
acyloxy-carbonyl products were synthesized using
the presented method makes the α-oxygenated
Cu/CuI/air,[
51]
Cu(acac)
complex
/TBHP,
[52]
CuI/O
[53]
2
,
ketones
with
the
pendant
carboxylic-acid
2
[54]
Pybox–Cu(II)
/
K
4
[Fe(CN)
6
],
functionality in the α-acyloxy substituent.
[
55]
[56]
TBAI/H O
2 2
or TBAI/TBHP, hypervalent iodine
To get a deeper insight into the oxidative C-O
coupling of malonyl peroxides with silyl enol ethers,
we investigated the α-acyloxylation of acetophenone
derived silyl enol ether 2a using cyclopropyl malonyl
peroxide 4a both as the oxidant and the O-component
(Table 1). To obtain product 5aa with maximum
[57]
compounds,
N-methyl-O-benzoylhydroxylamine
hydrochloride,[ or TBAI / electric current. Apart
58]
[59]
from these reports, α-oxygenation of mono-carbonyl
[60]
compounds were achieved by hydroxylation
and
alkoxylation[ of silyl enol ethers, hydroxylation
61]
[62]
[61c, 63]
and alkoxylation
of alkyl enol ethers or
these processes of
yields, the reaction mixture was treated by NH
aqueous solution after the reaction was complete.
4
Cl
enolates.[
64]
All
oxyfunctionalization require addition of an external
oxidant into the reaction, which usually plays
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201900271
Scheme 3. Preparation of silyl enol ethers 2a-r and methyl enol ethers 3m, 3o, 3s, 3t from ketones 1a-t. Synthesis of α-
acyloxyketones 5aa-ra, 5ab, 5ac from silyl enol ethers 2a-r and peroxides 4a-c and α’-acyloxyenol ethers 6ma, 6oa, 6sa,
6
ta from methyl enol ethers 3m, 3o, 3s, 3t and malonyl peroxide 4a.
Firstly, silyl enol ether 2a was converted into C-O
coupling product 5aa in CH Cl as a solvent (Table 1,
Table 1. Optimization of the oxidative C-O coupling of
2
2
a)
cyclopropyl malonyl peroxide 4a with silyl enol ether 2a.
entries 1-2). However, there was only 43% yield of
aa within 5 h, which did not significantly increase
with time (24 h, 46%, entry 2). When the reaction
was performed in CH CN, Et O, THF for 5 h (entries
-5) the best result was achieved in THF (68 %, entry
). The increase of the reaction time to 24 h did not
5
3
2
3
5
Entry
Solvent
Time, h
Yield
aa, %
lead to a significant increase in yield (entry 6). The
5-92 % yields of 5aa were achieved with 1.5 eq. of
malonyl peroxide 4a and THF, dioxane or EtOAc as
a solvent for 5 h (entries 7-9). Acetone and CHCl
resulted 5aa in 58 % and 53 % yields (entries 10 and
1). The attempt to improve the yield of 5aa
5
8
1
2
3
4
5
6
7
8
9
1
1
CH
CH
CH
2
2
3
Cl
Cl
CN
2
5
24
5
5
5
24
5
5
5
5
43
46
45
53
68
70
92
89
85
58
53
30
2
3
2
Et O
1
THF
THF
THF
1,4-dioxane
EtOAc
acetone
CHCl
-
performing the reaction without a solvent led to poor
result (entry 12). The main by-product in entries 1-11
was starting acetophenone 1a as a result of 2a
hydrolysis.
b)
b)
b)
With the optimized conditions in hand (Table 1,
entry 7), we next explored the substrate scope to
demonstrate the generality of the α-acyloxylated
ketones 5 synthesis via the oxidative C-O coupling of
malonyl peroxides 4 with silyl enol ethers 2. To
improve the procedure, we decided to perform the
whole sequence of ketones 1 transformations into the
final products without the time-consuming isolation
b)
0
1
2
b)
3
5
2
b), c)
1
a)
General procedure: Cyclopropyl malonyl peroxide 4a
(
1.2 mmol, 153.6 mg) was added to a solution of 2a (1.0
mmol, 192.3 mg) in a solvent (2 mL). Reaction mixture
was stirred for 5 or 12 h at 20-25 °C then treated by NH Cl
4
b)
[69]
aq. solution. 1.5 mmol (192.2 mg) cyclopropyl malonyl
peroxide 4a. reaction without solvent at 90 °C, for 2 h.
and purification of enol ethers. For this purpose,
c)
the ketones
1
were silylated using
a
[70]
chlorosilane/NaI/NEt
3
combination, and crude silyl
enol ethers 2 produced in virtually quantitative yields,
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201900271
were subjected to further reactions with malonyl
peroxides 4 without purification (Scheme 4).
mmol, 192.2-363.3 mg), THF (2 mL), 5 h, 0 °C → 20-
25 °C. 4) treatment by NH
4
Cl aq. solution. Isolated yield of
5
aa-ra, 5ab, 5ac based on ketone 1a-r.
The α-acyloxylated aryl ketones 5aa-ka were
obtained in 50% (for 5ja) to 83% (for 5aa) yields
excepting the product 5da prepared from 2-
chloroacetophenone 1d (35%). The influence of
electron-donating
or
electron-withdrawing
substituents on the products 5aa-ka yields was not
observed. The products 5la-oa from the aliphatic
ketones 1l-o were prepared in 65-85 % yields.
Presence of benzylic or thienyl group increases the
yields of α-acyloxylated ketones, the products 5pa-ra
were obtained in 69-77% yields. The flexibility of
this approach in selection of starting materials is
illustrated by facile formation of the product 5ra
from easily oxidizable thiophene-containing ketone
1
r. Phthaloyl peroxide 4c resulted in α-acyloxy
ketone 5ac with 88 % yield.
We further examined the possibility of smooth
hydrolysis of the C-O coupling product 5ia with
formation of the α-hydroxy ketone 7i and found that
the malonate derivative 5ia can be easily transformed
into 7i with 98 % yield (Scheme 5).
Scheme 5. Hydrolysis of the product 5ia to form the α-
hydroxy ketone 7i.
The reaction of cyclopropyl malonyl peroxide 4a
with methyl enol ethers 3m in optimized conditions
(
Table 1, entry 7) did not lead to product 5ma.
Instead, unexpected cyclic oxidative C-O coupling
product 8ma was detected in the reaction mixture by
NMR (see SI). After exclusion of “treatment by
NH Cl aq. solution“ step and a slight changes in the
4
conditions of coupling of cyclopropyl malonyl
peroxide 4a with methyl enol ethers 3m, we were
able to isolate the cyclic product 8ma in individual
state with 15% yield (Scheme 6). The second product
in the reaction was truly remarkable - unstable
compound 6ma containing both carboxylic acid and
enol fragment was isolated with 9% yield. It was
shown that cyclic product 8ma rearranges into 6ma
in acidic conditions (Scheme 6).
Scheme 4. Synthesis of α-acyloxylated ketones 5 from
ketones 1. Reaction conditions: 1) ketone 1 (98.2-238.3 mg,
1
(
1
2
.0 mmol, 1.0 eq.), NaI (210 mg, 1.4 mmol, 1.4 eq.), Et
152 mg, 1.5 mmol, 1.5 eq.), Me SiCl (165.0 μL, 141.2 mg,
CN (1 mL), 12 h, 0 °C → 20-25 °C.
) isolation of crude silyl enol ether. 3) peroxide 4 (1.5
3
N
3
.3 mmol, 1.3 eq.), CH
3
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201900271
methyl enol ethers 3 acid-catalyzed rearrangement of
the intermediate 8 yields the α-acyloxy enol ethers 6
(
see Scheme 6).
Scheme 6. Oxidative C-O coupling of malonyl peroxide 4a
with methyl enol ether 3ma with the formation of
unexpected products 8ma and 6ma.
When we carried out TsOH-catalyzed reaction of
malonyl peroxide 4a with methyl enol ethers 3, we
were surprised to observe selective unusual oxidative
transformation – oxidative C-O coupling with
retaining of easily oxidizable enol fragment (Scheme
7
). The liable C-O coupling products 6 containing
both carboxylic acid and enol fragment were
synthesized from cyclopropyl malonyl peroxide 4a
and methyl enol ethers 3 with 49-64% yields
(
Scheme 7).
Scheme 8. Proposed reaction mechanism of C-O coupling
products formation.
This mechanistic pathway is consistent with
previous investigations of the reactivity of the
[6b, 6e]
malonyl peroxides 4.
Based on the obtained
results we can consider the discovered oxidative C-O
coupling of malonyl peroxides with enol ethers as
oxidative [5+2] cycloaddition from the formal point
of view.
Conclusion
Scheme 7. Oxidative C-O coupling of malonyl peroxide 4a
with methyl enol ethers 3 with retaining of enol fragment.
In summary, we disclosed oxidative C-O coupling of
malonyl peroxides with enol ethers proceeding via
oxidative [5+2] cycloaddition. Traditional Rubottom
oxidation of enol ethers with the formation of solely
active oxygen atom transfer products was not
observed. From the silyl enol ethers, the α-acyloxy
ketones were prepared with 35-88 % yields. In the
case of methyl enol ethers unusual oxidative
transformation was observed – oxidative C-O
coupling with retaining of easily oxidizable enol
fragment. The paradoxical situation of saving of enol
double bond in the oxidative process illustrates the
unlimited possibilities of malonyl peroxides in
organic synthesis. Convenient one-pot method for the
preparation of the α-acyloxyketones with a free
carboxylic acid group from ketones with yields 35-
88% on two steps via silyl enol ethers formation and
oxidation was developed.
Suggesting a mechanism, we believe that the
reaction proceeds as outlined in Scheme 8. The
nucleophilic attack by the double bond of the enol
[71]
ether 2 or 3 on a weak peroxide bond resulted in
unstable cyclic acetal A (detected by NMR in CDCl
solution, see SI) in the case of silyl enol ethers 2 or
3
isolable cyclic acetal 8[
6a, 7]
in the case of methyl enol
ethers 3. The unstable cyclic acetal A could not be
isolated in pure form even though formation of
acetals from peroxides is general favorable due to
greater strength of the C-O vs. O-O bond and
stabilization by the anomeric effect.[72] Hydrolysis of
A results in the α-acyloxy ketones 5. In acidic
[3]
conditions cyclic acetal A is transformed into the α-
acyloxy ketones 5 (see SI) with abstraction of
trimethylsilyl group as Si(CH
3
) cation elimination is
3
[73]
more favorable than deprotonation. In the case of
Experimental Section
5
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Advanced Synthesis & Catalysis
10.1002/adsc.201900271
Experimental Procedures for Table 1.
reduced pressure using a rotary evaporator (15-20 mmHg),
(
bath temperature, ca. 20‒25 °C). The product 7i was
isolated by column chromatography on SiO
from 20:1 to 2:1).
2
(PE:EtOAc =
Experimental Procedure for Table 1, entries 1-11.
Cyclopropyl malonyl peroxide 4a (1.2-1.5 mmol, 153.6-
Experimental Procedures for Scheme 6.
1
92.2 mg, 1.2-1.5 eq.) was added to a solution of 2a (1.0
mmol, 192.3 mg, 1.0 eq.) in CH
,4-dioxane, EtOAc, acetone, CHCl
reaction mixture was stirred for 5 or 24 h at 20-25 °C.
Later, saturated aqueous NH Cl (10 mL) was added, the
mixture was extracted with CH Cl (3×15 mL), dried over
Na SO , filtered and concentrated under reduced pressure
using rotary evaporator (15-20 mmHg), (bath
temperature, ca. 20‒25 °C). Product 5aa was isolated by
column chromatography on SiO (CH Cl :EtOAc = from
5:1 to 5:1).
2
Cl
2
, CH
3 2
CN, Et O, THF,
1
3
(2 mL) at 0-5 °C. The
Methyl enol ether 3ma (1.0 mmol, 112.2 mg, 1.0 eq.) was
added to a solution of malonyl peroxide 4a (1.0 mmol,
4
2 2
128.1 mg, 1.0 eq.) in CH Cl (2 mL) at 0-5 °C. The
2
2
reaction mixture was stirred 30 min. at 20-25 °C. After that
2
4
the reaction mixture was transferred onto SiO
2
a
chromatographic column and products 8ma and 6ma were
isolated with use of mixture PE:EtOAc (7:1) as eluent.
2
2
2
1
TsOH-catalyzed rearrangement of 8ma into 6ma.
Experimental Procedure for Table 1, entry 12.
p-TsOH·H
solution of 8ma (0.2 mmol, 48.1 mg, 1.0 eq) in CH
mL). The reaction mixture was stirred 10 min. at 20-25 °C.
2
O (0.01 mmol, 1.9 mg, 0.05 eq.) was added to a
2
2
Cl (2
Cyclopropyl malonyl peroxide 4a (1.5 mmol, 192.2 mg,
1
0
.5 eq.) was added to 2a (1.0 mmol, 192.3 mg, 1.0 eq.) at
After that the reaction mixture was transferred onto SiO
2
-5 °C. The reaction mixture was stirred for 2h at 90 °C.
chromatographic column and product 6ma (68%, 32.7 mg,
0.14 mmol) was isolated with use of mixture PE:EtOAc
(7:1) as eluent.
After cooling to room temperature saturated aqueous
NH
CH
4
Cl (10 mL) was added, the mixture was extracted with
2 2 2 4
Cl (3×15 mL), dried over Na SO , filtered and
concentrated under reduced pressure using a rotary
evaporator (15-20 mmHg), (bath temperature, ca.
Experimental Procedure for Scheme 7.
2
0‒25 °C). Product 5aa was isolated as described above.
p-TsOH·H
2
O (0.05 mmol, 9.5 mg, 0.05 eq.) was added to a
solution of malonyl peroxide 4a (1.1 mmol, 141.0 mg, 1.1
Experimental Procedure for Scheme 4.
2 2
eq.) in CH Cl (2 mL). Later, methyl enol ether 3 (1.0
mmol, 112.2-142.2 mg, 1.0 eq.) was added dropwise with
stirring at 0-5 °C. The reaction mixture was stirred for 10
min. at 20-25 °C. After that the reaction mixture was
Preparation of silyl enol ethers 2.[70]
2
transferred onto SiO chromatographic column and the
NaI (1.4 mmol, 210.0 mg, 1.4 eq.) was placed in a round
bottom flask and dried under vacuum (15-20 mmHg) using
a heat gun (gun temperature 100-150 °C) for 5 min. After
cooling to room temperature, the flask was filled with
product 6 was isolated with the use of mixture PE:EtOAc
7:1) as eluent.
(
argon. Then, CH
and Et
added. The mixture was cooled with an ice/water bath, and
Me SiCl (1.3 mmol, 141.2 mg, 165.0 μL, 1.3 eq.) was
3
CN (1 mL), ketone 1 (1.0 mmol, 1.0 eq.),
3
N (1.5 mmol, 151.8 mg, 1.5 eq.) were successively
Acknowledgements
3
added at 0 °C. The cooling bath was removed, and the
mixture was stirred for 12 h at room temperature. Then,
volatile components were evaporated under reduced
pressure using a rotary evaporator (15-20 mmHg), (bath
temperature, ca. 40‒45 °C). The solid residue was washed
with hexane (3×15 mL) (the hexane layers were decanted
and filtered through a cotton plug). The combined filtrates
were concentrated under reduced pressure using a rotary
evaporator (15-20 mmHg), (bath temperature, ca.
Synthesis and experimental studies were supported by the
Russian Foundation for Basic Research (Grant no 18-33-00651).
Authors are grateful to Department of Structural Studies,
Zelinsky Institute of Organic Chemistry RAS for HRMS analysis.
References
2
0‒25 °C), furnishing the silyl enol ether 2 which was used
[
1] a) C.-J. Li, Acc. Chem. Res. 2009, 42, 335-344; b) C. S.
Yeung, V. M. Dong, Chem. Rev. 2011, 111, 1215-
without purification.
1
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C-O coupling of malonyl peroxides 4 with silyl enol ethers
Beilstein J. Org. Chem. 2015, 11, 92-146.
2
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[
2] a) A. O. Terent'ev, V. A. Vil', G. I. Nikishin, W. Adam,
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Peroxide 4 (1.5 mmol, 192.2-363.3 mg, 1.5 eq.) was added
to a solution of crude silyl enol ether 2 in dry THF (2 mL)
at 0-5 °C. The reaction mixture was stirred 5 h at 20-25 °C.
Later, saturated aqueous NH
mixture was extracted with CH
Na SO , filtered and concentrated under reduced pressure
using rotary evaporator (15-20 mmHg), (bath
temperature, ca. 20‒25 °C). Products 5aa-ra, 5ab were
isolated by column chromatography on SiO
4
Cl (10 mL) was added, the
2
2
Cl (3×15 mL), dried over
2
4
a
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2 2
CH Cl :EtOAc = from 30:1 to 5:1). Product 5ac was
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FULL PAPER
C-O coupling of malonyl peroxides with enol
ethers via [5+2] cycloaddition: non-Rubottom
oxidation
Adv. Synth. Catal. Year, Volume, Page – Page
Vera A. Vil’, Evgenii S. Gorlov, Oleg V. Bityukov,
Yana A. Barsegyan, Yulia E. Romanova, Valentina
M. Merkulova and Alexander O. Terent’ev*
1
0
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