Organocatalytic peroxidation of malonates, β-ketoesters, and cyanoacetic esters using n-Bu4NI/t-BuOOH-mediated intermolecular oxidative C(sp3)-O coupling

Article abstract of DOI:10.1016/j.tet.2015.09.047

A new organocatalytic approach for the synthesis of peroxides based on CH activation of a sp³-hybridized carbon atom is reported. Peroxides were prepared in 31-89% yield by the reaction of malonates, β-ketoesters, and cyanoacetic esters with a Bu₄NI/tert-butyl hydroperoxide system. The formation of the expected hydroxylation products was not observed. In the discovered reaction, tert-butyl hydroperoxide plays a dual role by acting as the oxidant and the O-reagent for the C-O coupling. The synthesis can be scaled up to generate gram quantities of the target products.

Full text of DOI:10.1016/j.tet.2015.09.047

Accepted Manuscript
Organocatalytic peroxidation of malonates, β-ketoesters, and cyanoacetic esters
3
using n-Bu NI / t-BuOOH-mediated intermolecular oxidative C(sp )–O coupling
4
Alexander O. Terent’ev, Alexander T. Zdvizhkov, Dmitri O. Levitsky, Fabrice Fleury,
Roman A. Pototskiy, Alena N. Kulakova, Gennady I. Nikishin
PII:
S0040-4020(15)30075-2
10.1016/j.tet.2015.09.047
TET 27144
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 14 July 2015
Revised Date: 8 September 2015
Accepted Date: 21 September 2015
Please cite this article as: Terent’ev AO, Zdvizhkov AT, Levitsky DO, Fleury F, Pototskiy RA, Kulakova
AN, Nikishin GI, Organocatalytic peroxidation of malonates, β-ketoesters, and cyanoacetic esters using
3
n-Bu NI / t-BuOOH-mediated intermolecular oxidative C(sp )–O coupling, Tetrahedron (2015), doi:
4
10.1016/j.tet.2015.09.047.
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ACCEPTED MANUSCRIPT
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Organocatalytic peroxidation of malonates,
Leave this area blank for abstract info.
β-ketoesters, and cyanoacetic esters using n-
Bu NI / t-BuOOH-mediated intermolecular
4
3
oxidative C(sp )–O coupling
Alexander O. Terent’ev,* Alexander T. Zdvizhkov, Dmitri O. Levitsky, Fabrice Fleury, Roman A.
Pototskiy, Alena N. Kulakova, Gennady I. Nikishin
N.D. Zelinsky Institute of Organic Chemistry, Leninsky Prospect 47, Moscow, 119991; UFIP CNRS UMR
286, Mechanism and regulation of DNA repair team Université de Nantes, 2 rue de la Houssinière, 44322
a
a
b
b
a
a
a
a
b
6
O
t
O
Bu OOH, n-Bu NI
4
R
R
OEt
OEt R = COOEt, C(O)CH , CN
3
R' OOBut
R'
H

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Organocatalytic peroxidation of malonates, β-ketoesters, and cyanoacetic esters using
3
n-Bu NI / t-BuOOH-mediated intermolecular oxidative C(sp )–O coupling
4
a
a
b
b
Alexander O. Terent’ev, Alexander T. Zdvizhkov, Dmitri O. Levitsky, Fabrice Fleury, Roman A.
a
a
a
Pototskiy, Alena N. Kulakova, Gennady I. Nikishin
a
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow, 119991, Russian Federation
UFIP CNRS UMR 6286, Mechanism and regulation of DNA repair team Université de Nantes, 2 rue de la Houssinière, 44322, France
b
ARTICLE INFO
ABSTRACT
3
Article history:
Received
A new organocatalytic approach for the synthesis of peroxides based on СН activation of a sp -
hybridized carbon atom is reported. Peroxides were prepared in 31 – 89 % yield by the reaction
Received in revised form
Accepted
Available online
4
of malonates, β-ketoesters, and cyanoacetic esters with a Bu NI / tert-butyl hydroperoxide
system. The formation of the expected hydroxylation products was not observed. In the
discovered reaction, tert-butyl hydroperoxide plays a dual role by acting as the oxidant and the
O-reagent for the C-O coupling. The synthesis can be scaled up to generate gram quantities of
the target products.
Keywords:
Peroxides
Oxidative coupling
Organocatalysis
Malonates
2
009 Elsevier Ltd. All rights reserved.
Tetra-n-butylammonium iodide
dicarbonyl compounds at the α-position by tert-butyl
1
. Introduction
[7a,b]
hydroperoxide.
In this study, we performed the
organocatalytic peroxidation of malonates, β-ketoesters, and
Organic peroxides are widely used as radical polymerization
cyanoacetic esters at the α-position using the Bu NI / tert-butyl
4
initiators in the industrial synthesis of polymers such as
polystyrene, polyvinyl chloride, polyacrylates, and polyethylene.
A wide variety of commercial monomers and their composites
requires for polymerization a wide assortment of peroxides, the
hydroperoxide system. This is a new approach for the synthesis
3
of peroxides based on СН activation of a sp -hybridized carbon
atom, which is generally accomplished by autooxidation, or
under the action of hydroperoxides combined with variable-
valence metal ions. Until recently, only the following two
most
well-known
of
which
are
peroxy
esters,
peroxydicarbonates, peroxycarbonates, peracetals, cyclic
triperoxides, organic hydroperoxides, dialkyl peroxides, diacyl
examples of peroxidation by the Bu NI / tert-butyl hydroperoxide
4
[
1,2]
system were described: the synthesis of peroxy esters from
peroxides, and geminal bishydroperoxides.
In the past
2
[8a]
aldehydes (СН activation of a sp -hybridized carbon atom)
and the peroxidation of C−H bonds adjacent to the amide
decades, organic peroxides have received attention from
researchers in the field of medicinal chemistry because these
3
[8b]
[
3]
nitrogen (СН activation of a sp -hybridized carbon atom).
compounds were found to possess pronounced antimalarial,
[
4]
[5]
anthelmintic, and antitumor activities. Peroxides obtained
from lower aldehydes and ketones are attracting interest also as
The Bu NI / tert-butyl hydroperoxide system has been
4
[
9]
extensively studied in recent years. It is assumed that a number
of various reactive species are generated in this system, such as
O-centered radicals and oxidized iodine species. Owing to this
fact, this system is used in the oxidative synthesis resulting in the
[
6]
explosive compounds.
The preparation of radical polymerization initiators and
biologically active compounds is the major impetus for the
development of new methods for the synthesis of peroxides. The
present study is a part of our continuing research on the
[
10]
[11]
[12]
[9f, 13]
formation of C-C, C-N, C-S and C-O
bonds.
[
7]
peroxidation of dicarbonyl compounds. Earlier, it has been
found that transition metals catalyze the peroxidation of β-
—
——

Corresponding author. Tel.: +7-916-385-4080; fax: +7-499-135-5328; e-mail: terentev@ioc.ac.ru

2
Tetrahedron
2
. Results and discussion
ethanol, 1,2-dichloroethane, and dimethylformamide, the yield of
ACCEPTED MANUSCRIPT
2
d was much lower (entries 5-7). In entries 8-10, other iodine-
Malonates 1a-h, β-ketoesters 3a-d, and cyanoacetic esters 5a-
containing catalysts were examined, the related Me NI (entry 8)
4
d substituted at the α-position were used as the starting reagents
for the synthesis of target peroxides 2a-h, 4a-d, 6a-d (Scheme 1).
proved to be a good catalyst, whereas peroxidation in the
presence of I (entry 9) and KI (entry 10) was negligible. Using
2
the optimised reaction conditions of entry 2 (Table 1), peroxides
2a-h, 4a-d, 6a-d were synthesized (Table 2).
O
O
t
Bu OOH / cat
R
R
OEt
OOBut
OEt
R'
Solvent
Table 2. Structures and yields of peroxides 2a-h, 4a-d, and
R'
6
a-d.
1
3
5
a-h
a-d
a-d
2a-h
4a-d
6a-d
O
O
O
O
EtO
OEt
Me OOBut
EtO
2b, 73
EtO
OEt
1
1
1
1
1
1
1
1
3
3
3
3
5
5
5
5
a, 2a: R = COOEt, R' = Me;
b, 2b: R = COOEt, R' = Et;
c, 2c: R = COOEt, R' = n-Bu;
d, 2d: R = COOEt, R' = Bn;
e, 2e: R = COOEt, R' = allyl;
f, 2f: R = COOEt, R' = Ph;
Et OOBut
2
a, 76
O
O
O
O
g, 2g: R = COOEt, R' = CH CH C(O)CH ;
2
2
3
h, 2h: R = COOEt, R' = CH CH CN;
EtO
OEt
OEt
2
2
n-Bu OOBut
t
a, 4a: R = CH C=O, R' = Me;
OOBu
3
Bn
b, 4b: R = CH C=O, R' = n-Bu;
3
c, 4c: R = CH C=O, R' = Bn;
3
a
2
c, 83
2d, 85 (81)
d, 4d: R = CH C=O, R' = CH CH C(O)CH ;
3
2
2
3
a, 6a: R = CN, R' = Bu;
b, 6b: R = CN, R' = Bn;
c, 6c: R = CN, R' = allyl;
O
O
O
O
EtO
OEt
d, 6d: R = CN, R' = CH CH COOEt
2
2
t
EtO
OEt
OOBu
Scheme 1. Synthesis of peroxides from malonates 1a-h, β-
ketoesters 3a-d, and cyanoacetic esters 5a-d.
Ph OOBut
2
e, 67
2f, 89
A search for the conditions of peroxidation of diethyl
benzylmalonate 1d to form diethyl 2-benzyl-2-(tert-
butylperoxy)malonate 2d was performed using the catalysts
Bu NI, Me NI, I , and KI in CH CN, EtOH, DMF,
O
O
O
O
EtO
NC
OEt
OOBut
EtO ( )2
O
OEt
t
4
4
2
3
OOBu
1
,2-dichloroethane, and benzene (Table 1).
Table 1. Peroxidation of diethyl benzylmalonate 1d by tert-
butyl hydroperoxide.
2
g, 83
2h, 83
O
O
O
O
t
Bu OOH / cat
O
O
O
O
EtO
OEt
EtO
OEt
Solvent
Bn OOBut
OEt
OEt
Bn
Me OOBut
Bun OOBut
1
d
2d
Entry Catalyst,
Solvent
Yield of 2d, %
4
4
6
a, 38
4b, 47
%
mol
O
O
O
O
1
2
3
4
5
6
7
8
9
1
Bu
Bu
Bu
Bu
Bu
Bu
Bu
4
4
4
4
4
4
4
NI, 50
NI, 20
NI, 10
NI, 20
NI, 20
NI, 20
NI, 20
CH
CH
CH
3
3
3
CN
CN
CN
80
OEt
Bn OOBut
OEt
85
( )2
t
OOBu
60
O
4d, 33
PhH
44
c, 35
EtOH
19
O
O
N
N
1,2-Dichloroethane
DMF
16
OEt
OEt
traces
83
Bun OOBut
Bn OOBut
Me
, 50
KI, 50
4
NI, 50
CH
CH
CH
3
3
3
CN
CN
CN
a, 35
6b, 39
I
2
traces
traces
0
O
N
O
t
General reaction conditions: 78-80 °С, 6 h, 3 mol of 70% aq. Bu OOH per
mole of 1d
N
OEt
OOBut
OEt
t
EtOOC ( ) OOBu
2
In entries 1-3, performed in CH CN, the effect of the amount
3
of the catalyst was studied; a 20% loading of the catalyst with
respect to 1d was found to be the optimal amount (entry 2). In
entries 4-7, the possibility of using other solvents was examined;
a moderate result was obtained using benzene (entry 4), while in
6c, 31
6d, 42
a
The experiment was scaled up by increasing the amounts of the reagents by
a factor of five.

3
Based on the results presented in Table 2, itAcaCn CbeEcoPnTclEudDed MANTUheSpCubRlisIhPedTdata suggest that the reaction may proceed by
that the Bu NI-catalyzed peroxidation provides a versatile
two different pathways. One of them (pathway A) is based on the
4
approach to the synthesis of structurally different α-tert-
butylperoxy malonates 2a-h, β-ketoesters 4a-d, and cyanoacetic
esters 6a-d. The yield of the resulting α-peroxidated malonates
formation of t-BuOO• and t-BuO• radicals in the Bu NI / t-
4
BuOOH system followed by the generation of a C-centered
radical from malonic ester and the recombination of the latter
[
8]
2
a-h varies from 67 to 89%, or a range of substrates, including
radical with the t-BuOO• radical to form the target peroxide.
Another pathway (pathway B) involves the oxidation of Bu NI to
those containing reactive groups, such as CH in the benzyl
2
4
+
-
+
-
moiety and the allyl, carbonyl and nitrile groups. The yields of
peroxides 4a-d and 6a-d, prepared from β-ketoesters 3a-d and
cyanoacetic esters 5a-d were approximately two times lower, in
comparison with 2a-h. Attempts to peroxidise β-diketones (3-
benzylpentane-2,4-dione and 3-butylpentane-2,4-dione) were
unsuccessful; only complex mixtures of products were obtained.
give [Bu N] [IO] and then [Bu N] [IO ] , which reacts with
4 4 2
+
malonic ester at the α-position to form [Bu N] [(COOEt) CH-
4
2
-
I(OH)O] . The final step is the replacement of hypervalent iodine
bound to the organic moiety by tert-butyl hydroperoxide
[
14]
(Scheme 2).
Plausible peroxidation mechanisms.
O
O
B
EtO
OEt
R
A
+
-
O
O
O
[
n-Bu N] [IO ]
4 2
R
I
t-BuOOH
n-Bu NI
t-BuO
+
EtO
OEt
-
OH + n-Bu N
t-BuOOH - t-BuOH
4
HO
4
1/2 I2
NBu -n
4
t-BuOOH
n-Bu NI
+
-
[
n-Bu N] [IO]
4
t-BuOO
H O
t-BuOOH +
4
-
OH + n-Bu N
2
4
t-BuOOH
O
O
O
O
O
O
t-BuO
t-BuOO
R
H O
2
EtO
OEt
EtO
OEt
EtO
OEt
OOBut
R
R
Scheme 2. Plausible peroxidation mechanisms in the example of malonates. Free radical pathway A and ionic pathway B.
Peroxide 10 is apparently formed via the abstraction of a
hydrogen atom from CH fragment with formation of С-centered
radical followed by the recombination of the latter radical with
the t-BuOO• radical. The benzylic position is traditionally
considered as a point for free radical reactions when free radical
initiators are applied. Another evidence to support pathway A
results from an additional experiment on catalyst isolation after
[
8]
[14]
Based on literature data, pathways A
and B
are
indirectly confirmed by the formation of dehydrogenated dimer 8
from malonic ester 7 (Scheme 3).
t
3
eq. Bu OOH
EtOOC
EtOOC
COOEt
COOEt
EtOOC
0
.2 eq Bu NI
4
peroxidation of diethyl benzylmalonate 1d. Bu NI was isolated in
4
CH CN,
EtOOC
3
Reflux
75% yield. In such a way pathway B seems to be less plausible,
7
8, 62%
[14]
however based on the literature data it cannot be excluded.
Scheme 3. Transformation of malonic ester 7 to tetraethyl
ethene-1,1,2,2-tetracarboxylate 8.
Apparently, the mechanism of Bu NI-mediated peroxidation of
4

-dicarbonyl compounds differs essentially from that of
transition metal-mediated peroxidation. In the metal-catalyzed
[7b]
C-centered radicals formed via pathway A can dimerize with
following oxidative dehydration with formation of product 8.
Product 8 can also be formed through nucleophilic substitution of
iodine-containing moiety by malonate anion in iodinated
intermediate prepared by pathway B with following oxidative
dehydration.
reaction following reactivity order was observed: -diketones>-
[
7b]
ketoesters>malonic esters.
reaction proceeds optimally with malonic esters, moderately with
-ketoesters, and peroxidations of -diketones were
unsuccessful.
On the contrary, Bu NI-mediated
4

3
. Conclusions
Evidence to support pathway A concludes in the formation of
9
9
-(tert-butylperoxy)-9-methyl-9H-fluorene 10 from 9-methyl-
H-fluorene 9 (Scheme 4).
A new approach is reported for the synthesis of peroxides
from malonates, β-ketoesters, and cyanoacetic esters using the
t
organocatalytic Bu NI / tert-butyl hydroperoxide system and
3
eq. Bu OOH
4
3
activation of a С(sp )-H bond. α-tert-Butyl peroxides were
0
.2 eq Bu NI
4
prepared in 31 – 89 % yields. The synthesis can be scaled up to
yield gram quantities of the target products.
CH CN,
3
Reflux
OOBut
4
. Experimental section
9
10, 92%
Scheme 4. Transformation of 9-methyl-9H-fluorene 9 in to 9-
tert-butylperoxy)-9-methyl-9H-fluorene 10.
Caution: Although we have encountered no difficulties in
working with peroxides, precautions, such as the use of
(

4
Tetrahedron
1
3
shields, fume hoods, and the avoidanceAoCf CheEatPinTg EanDd MA(qN, JUSC= R7.I1PTHz, 4H, OCH CH ). C NMR (75.48 MHz,
H-H
2
3
shaking, should be taken whenever possible.
CDCl ): δ = 14.0 (OCH CH ), 19.6 (CCH ), 26.4 (C(CH ) ), 61.7
3
2
3
3
3 3
1
(OCH
Calculated for C12
4.93;
C H O +Na] found 285.1315 (Δ = 2.1 ppm). IR (film): 1749
2
CH
3
), 80.8 (C(CH
3
)
3
), 84.9 (CH
3
C), 168.0 (CO).
Н NMR spectra were recorded on a Bruker AM300
1
13
H
22
O
6
: % C 54.95; % H 8.45; found: % C
instrument (300.13 MHz for H and 75.48 MHz for C) in a
CDCl solution. Commercial diethyl ethylmalonate 1b, diethyl
phenylmalonate 1f, diethyl malonate 7, ethyl methylacetoacetate
a, 9-methylfluorene 9, a 70 % aqueous solution of t-BuOOH,
5
[
%
H
8.43. HRMS-ESI: calculated 285.1309
3
1
2
22
6
-1
(
vs, υ ) cm .
CO
3
Bu NI, Me NI, I , and KI (Acros) were used as-is. Acetonitrile,
Diethyl (tert-butylperoxy)(ethyl)malonate 2b: Colorless oil.
H NMR (300.15 MHz, CDCl ): δ = 0.83 (t, J = 7.4 Hz, 3H,
4
4
2
1
1
,2-dichloroethane, and ethyl acetate (EA) were distilled over
3
H-H
P O before use. Benzene and petroleum ether (PE) (40/70) were
CH CH ), 1.19 (s, 9H, C(CH ) ), 1.21 (t, J = 7.1 Hz, 6H,
2
5
3
2
3 3
H-H
distilled over Na before use. Ethanol 96% was used without
additional purification. The filtration and column
chromatography were performed on silica gel (0.060–0.200 mm,
0 A, Acros); MeCN (HPLC grade) for ESI-HRMS experiments
OCH CH ), 2.13 (q, J = 7.4 Hz, 2H, CH CH ), 4.18 (q, J
=
2
3
H-H
2
3
H-H
1
3
7.1 Hz, 4H, OCH CH ). C NMR (75.48 MHz, CDCl ): δ = 7.2
2
3
3
(CH CH ), 14.1 (OCH CH ), 25.2 (CH CH ), 26.4 (C(CH ) ),
2
3
2
3
2
3
3 3
6
61.4 (OCH CH ), 80.5 (C(CH ) ), 87.8 (CH C), 167.4 (CO).
2 3 3 3 2
was purchased from Merck and was used as-is. High-resolution
mass spectra were recorded on a Bruker maXis instrument
equipped with an electrospray ionization (ESI) ion source. All
measurements were carried out in positive (+MS) ion mode
Calculated for C H O : % C 56.51; % H 8.75; found: % C
13 24 6
56.72;
%H
8.78.
HRMS-ESI:
calculated
299.1465
[
15]
[C H O +Na] found 299.1475 (Δ = 3.3 ppm). IR (film): 1748
1
3
24
6
-
1
(vs, υ ) cm .
CO
(
5
interface capillary voltage e 4500 V) with the m/z scan range of
0 - 3000. External calibration of the mass spectrometer was
Diethyl butyl(tert-butylperoxy)malonate 2c: Colorless oil.
1
H NMR (300.15 MHz, CDCl ): δ = 0.85 (t, J = 6.7 Hz, 3H,
3
H-H
performed with Electrospray Calibrant Solution (Fluka). The
direct syringe injection was used for all the analyzed solutions in
MeCN (flow rate 3 μL/min). Nitrogen was used as both the
nebulizer gas (0.4 bar) and the dry gas (4.0 L/min); the interface
temperature was set at 180 °C. Malonic esters 1a, 1c, 1d, 1e, 1g,
and 1h were prepared according to known procedures.
ketoesters 3b-d and cyanoacetic esters 5a-d were prepared as
described
CH (CH ) ), 1.20-1.26 (m, 21H, C(CH ) , (CH ) , OCH CH ),
3
2 3
3 3
13
2 3
2
3
4
.19 (q, JH-H = 7.1 Hz, 4H, OCH CH ). C NMR (75.48 MHz,
2
3
CDCl ): δ = 13.9 ((CH ) )CH ), 14.1 (OCH CH ), 22.6, 25.0,
3
2 3
3
2
3
3
1.8 (CH ), 26.4 (C(CH ) ), 61.6 (OCH CH ), 80.5 (C(CH ) ),
2
3 3
2
3
3 3
[
7b]
87.5 (CH
2
C), 167.6 (CO). Calculated for C15
H
28
O
6
: % C 59.19;
β-
%
H 9.27; found: % C 58.86; % H 9.23. HRMS-ESI: calculated
305.1959 [C15 +H] found 305.1958 (Δ = 0.3 ppm). IR
film): 1749 (vs, υCO) cm .
[
7a,b]
H O
28 6
.
-1
(
[
7b]
Diethyl benzyl(tert-butylperoxy)malonate 2d : Colorless
1
Synthesis of diethyl benzyl(tert-butylperoxy)malonate 2d
Table 1): To a solution of diethyl benzylmalonate 1d (0.50 g,
oil. H NMR (300.15 MHz, CDCl ): δ = 1.21 (t, J = 7.1 Hz,
3 H-H
(
6H, OCH CH ), 1.30 (s, 9H, C(CH ) ), 3.51 (s, 2H, CH Ph), 4.17
2 3 3 3 2
13
2
.00 mmol) in acetonitrile (10 mL) 70% t-BuOOH (0.77 g, 6.00
(q, JH-H = 7.1 Hz, 4H, OCH CH ), 7.23-7.27 (m, 5H, Ph).
C
2
3
mmol) was added. The mixture was heated to reflux, and then
Bu NI (0.07-0.37 g, 0.20-1.00 mmol), Me NI (0.20 g, 1.00
NMR (75.48 MHz, CDCl ): δ = 14.0 (OCH CH ), 26.6
3 2 3
(C(CH ) ), 37.8 (CH Ph), 61.7 (OCH CH ), 81.1 (C(CH ) ), 88.0
4
4
3 3
2
2
3
3 3
mmol), I (0.25 g, 1.00 mmol), or KI (0.17 g, 1.00 mmol) was
(CH C), 127.0, 128.0, 130.4, 135.0 (Ph), 167.0 (CO).
2
2
added. The solution was refluxed for 6 h. The solvent was
removed under water aspirator pressure. The suspension that
formed was diluted with diethyl ether (20 mL), and the
precipitate was filtered using silica gel. The solvent was removed
under water aspirator pressure. Product 2d was isolated by
chromatography on silica gel, eluting with PE-EtOAc (10/1).
[7b]
Diethyl allyl(tert-butylperoxy)malonate 2e : Colorless oil.
H NMR (300.15 MHz, CDCl ): δ = 1.22 (s, 9H, C(CH ) ), 1.24
1
3
3 3
(
t, JH-H = 7.2 Hz, 6H, OCH CH ), 2.91 (d, J = 7.1 Hz, 2H,
2
3
H-H
CHCH C), 4.20 (q, J = 7.2 Hz, 4H, OCH CH ), 5.03-5.14 (m,
2
H-H
2
3
13
2
(
H, CH =CHCH C), 5.52-5.87 (m, 1H, CH =CH). C NMR
2
2
2
75.48 MHz, CDCl ): δ = 14.1 (OCH CH ), 26.4 (C(CH ) ), 36.6
3 2 3 3 3
General conditions for synthesis of peroxides 2a-h, 4a-d,
(CH C), 61.6 (OCH CH ), 80.8 (C(CH ) ), 87.2 (CH C), 119.0
2 2 3 3 3 2
and 6a-d (Table 2): To a solution of malonate 1a-h, 3a-d, 5a-d
(CH =CH), 131.4 (CH =CH), 167.0 (CO).
2 2
(
2.00 mmol) in acetonitrile (10 mL), 70% t-BuOOH (0.77 g, 6.00
Diethyl (tert-butylperoxy)(phenyl)malonate 2f: Colorless
mmol) was added. The mixture was heated to reflux, and then
Bu NI (0.15 g, 0.40 mmol) was added. The solution was refluxed
for 6 h. Products 2a-h, 4a-d, and 6a-d were isolated as described
above.
1
oil. H NMR (300.15 MHz, CDCl ): δ = 1.26 (t, J = 7.2 Hz,
3
H-H
4
6
H, OCH CH ), 1.31 (s, 9H, CH ), 4.25 (q, J
= 7.2 Hz, 4H,
2
3
3
H-H
13
OCH CH ), 7.32-7.36 (m, 3H, Ph), 7.57-7.62 (m, 2H, Ph).
C
2
3
NMR (75.48 MHz, CDCl ): δ = 14.0 (OCH CH ), 26.5
3
2
3
Large-scale
synthesis
of
diethyl
benzyl(tert-
(C(CH ) ), 61.9 (OCH CH ), 81.5 (C(CH ) ), 88.2 (PhC), 127.2,
3 3 2 3 3 3
butylperoxy)malonate 2d (Table 2): To a solution of diethyl
benzylmalonate 1d (2.50 g, 10.1 mmol) in acetonitrile (50 mL),
128.0, 128.7, 134.6 (Ph), 166.8 (CO). Calculated for C H O : %
17 24 6
C 62.95; % H 7.46; found: % C 62.50; % H 7.59. HRMS-ESI:
7
0% t-BuOOH (3.86 g, 30.0 mmol) was added. The mixture was
calculated 347.1465 [C H O +Na] found 347.1462 (Δ=0.9
ppm). IR (film): 1750 (vs, υCO) cm .
1
7
24
6
-
1
heated to reflux, and then Bu NI (0.74 g, 2.00 mmol) was added.
4
The solution was refluxed for 6 h. The solvent was removed
under water aspirator pressure. The suspension that formed was
diluted with diethyl ether (100 mL), and the precipitate was
filtered using silica gel. The solvent was removed under water
aspirator pressure. Product 2d was isolated by chromatography
on silica gel, eluting with PE-EtOAc (10/1). Yield of 2d is (2.77
g, 8.20 mmol, 81 %).
[7b]
Diethyl (tert-butylperoxy)(3-oxobutyl)malonate 2g
:
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.19 (s, 9H,
= 7.2 Hz, 6H, OCH CH ), 2.10 (s, 3H,
COCH ), 2.41-2.50 (m, 4H, (CH ) ), 4.18 (q, J = 7.2 Hz, 4H,
C NMR (75.48 MHz, CDCl3): δ = 14.0
OCH CH ), 25.9 (COCH CH ), 26.4 (C(CH ) ), 29.9 (CH CO),
7.2 (COCH CH ), 61.8 (OCH CH ), 80.8 (C(CH ) ), 86.3
2 2 2 3 3 3
3
C(CH ) ), 1.22 (t, J
3
3
H-H
2 3
3
2 2
H-H
13
OCH CH ).
2
3
(
3
2 3 2 2 3 3 3
Diethyl (tert-butylperoxy)(methyl)malonate 2a: Colorless
(CH C), 167.1, 207.3 (CO).
2
1
oil. H NMR 300.15 MHz, CDCl ): δ = 1.22 (s, 9H, C(CH ) ),
3
3 3
1
.25 (t, JH-H = 7.1 Hz, 6H, OCH CH ), 1.66 (s, 3H,CCH ), 4.21
2 3 3

5
[7a]
[
7b]
Diethyl (tert-butylperoxy)(2-cyanoethyl)AmaCloCnaEtePT2Eh D: MANEUthSylCR2-(ItPerTt-butylperoxy)-2-cyanopent-4-enoate 6c
:
1
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.24 (s, 9H,
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.25 (s, 9H,
3
3
C(CH ) ), 1.27 (t, J = 7.0 Hz, 6H, OCH CH ), 2.37-2.62 (m,
(CH ) C), 1.29 (t, J = 7.2 Hz, 3H, OCH CH ), 2.69 (d, J
=
3
3
H-H
2
3
3 3
H-H
2
3
H-H
13
4
H, CH CH CN), 4.25 (q, J
= 7.0 Hz, 4H, OCH CH ).
C
7.4 Hz, 2H, CH ), 4.25 (q, J = 7.2 Hz, 2H, OCH CH ), 5.16-
2 H-H 2 3
13
2
2
H-H
2
3
NMR (75.48 MHz, CDCl ): δ = 11.4 (CH CH CN), 14.0
5.28 (m, 2H, CH =CH), 5.65-5.88 (m, 1H, CH =CH). С NMR
2 2
3
2
2
(
(
(
OCH CH ), 26.4 (C(CH3)3), 27.9 (CH CH CN), 62.4
(75.48 MHz, CDCl ): δ = 14.1 (OCH CH ), 26.3 (C(CH ) ), 39.6
(CH ), 63.1 (OCH CH ), 81.6 (C(CH ) ), 82.8 (CH С), 116.1
2 2 3 3 3 2
2
3
2
2
3 2 3 3 3
OCH CH ), 81.5 (C(CH ) ), 85.6 (CH C), 119.1 (CN), 166.2
2
3
3 3
2
CO).
(CN), 122.1 (CH=CH ), 130.6 (CH=CH ), 165.1 (CO).
2
2
[
7a]
Ethyl 2-(tert-butylperoxy)-2-methyl-3-oxobutanoate 4a:
Diethyl 2-(tert-butylperoxy)-2-cyanopentanedioate 6d
:
1
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.22 (s, 9H,
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.19-1.35 (m,
3
3
(
CH ) C), 1.23 (t, J
= 6.7 Hz, 3H, OCH CH ), 1.54 (s, 3H,
6H, OCH CH ), 1.24 (s, 9H, C(CH ) ), 2.28-2.59 (m, 4H,
3
3
H-H
2
3
2
3
3 3
CH COOBu-t), 2.25 (s, 3H, CH CO), 4.17 (q, J = 6.7 Hz, 2H,
CH CH CO), 4.12, (q, J = 6.9 Hz, 2H, OCH CH ), 4.29 (q, J
2 2 H-H 2 3 H-
13
3
3
H-H
1
3
OCH CH ).
C
NMR (75.48 MHz, CDCl3):
δ
=
14.0
= 6.9 Hz, 2H, OCH CH ). С NMR (75.48 MHz, CDCl ): δ =
H 2 3 3
2
3
(
OCH CH ), 18.3 (CH C), 25.7 (CH CO), 26.4 (C(CH ) ), 61.7
14.0, 14.2 (OCH CH ), 26.3 (C(CH ) ), 28.6, 30.5 (CH CH ),
2
3
3
3
3 3
2 3 3 3 2 2
(
OCH CH ), 80.8 (C(CH ) ), 89.7 (CH C), 168.1, 203.8 (CO).
61.0, 63.3 (OCH CH ), 81.0 (C(CH ) ), 82.9 (CH C), 115.9
2 3 3 3 2
2
3
3 3
3
Calculated for C H O : % C 56.88; % H 8.68; found: % C
(CN), 165.1, 171.1 (CO).
1
1
20
5
5
7.00;
%
H
8.69. HRMS-ESI: calculated 255.1203
t
Reaction of malonic ester with the Bu NI / Bu OOH
4
[
C H O +Na] found 255.1212 (Δ = 1.5 ppm). IR (film): 1752
1
1
20
5
-
1
system: t-BuOOH 70 % (0.77 g, 6.00 mmol) was added to the
solution of diethylmalonate 7 (0.32 g, 2.00 mmol) in acetonitrile
(10 mL). The mixture was heated to boiling and Bu NI (0.15 g,
(vs, υ ), 1735 (vs, υ ) cm .
CO CO
[
7b]
Ethyl
2-acetyl-2-(tert-butylperoxy)hexanoate
4b
:
4
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 0.86 (t, J
=
0.40 mmol) was added. The solution was refluxed for 6 hours.
3
H-H
6
.9 Hz, 3H, CH ), 1.15-1.45 (m, 7H, CH CH , OCH CH ), 1.25
Product 8 was isolated as described for 2d. Yield of 8 is (0.20 g,
3
2
2
2
3
(
s, 9H, (CH ) C), 2.00-2.25 (m, 2H, CH C), 2.23 (s, 3H,
0.60 mmol, 62 %).
3
3
2
1
3
CH CO), 4.18 (q, J
= 7.2 Hz, 2H, OCH CH ). C NMR
[17]
3
H-H
2
3
Tetraethyl ethene-1,1,2,2-tetracarboxylate 8.
crystals. m.p. 54–55 °C. Rf: 0.16 (1/10 EA / PE). H NMR
White
(75.48 MHz, CDCl ): δ = 13.9 (CH ), 14.1 (OCH CH ), 22.8,
1
3
3
2
3
2
5.0 (CH ), 26.2 (CH CO), 26.5 (C(CH ) ), 30.9 (CH ), 61.5
2 3 3 3 2
(
300.15 MHz, CDCl ): δ = 1.31 (t, J = 7.2 Hz, 12H, CH ), 4.31
3 H-H 3
13
(OCH CH ), 80.6 (C(CH ) ), 92.2 (CH C), 167.7, 203.7 (CO).
2
3
3 3
2
(q, JH-H = 7.2 Hz, 8H, CH2). C NMR (75.48 MHz, CDCl ): δ =
3
[
7b]
Ethyl 2-benzyl-2-(tert-butylperoxy)-3-oxobutanoate 4c
:
13.9 (CH ), 62.6 (CH ), 135.5 (C=C), 162.4 (CO). HRMS-ESI:
3 2
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.23 (t, J
=
calculated 339.1050 [C H O +Na] found 339.1046 (Δ = 1.1
14 20 8
3
H-H
7
.2 Hz, 3H, OCH CH ), 1.32 (s, 9H, (CH ) C), 1.90 (s, 3H,
ppm).
2
3
3 3
CH CO), 3.31 (d, J
= 14.4 Hz, 1H, CH Ph), 3.62 (d, J
=
3
H-H
2
H-H
Reaction of 9-methyl-9H-fluorene with the Bu NI /
Bu OOH system: t-BuOOH 70 % (0.77 g, 6.00 mmol) was
added to the solution of 9-methyl-9H-fluorene 9 (0.36 g, 2.00
mmol) in acetonitrile (10 mL). The mixture was heated to boiling
4
1
7
4.4 Hz, 1H, CH Ph), 4.17 (q, J
.15-7.32 (m, 5H, Ph). C NMR (75.48 MHz, CDCl ): δ = 14.0
= 7.2 Hz, 2H, OCH CH ),
t
2
H-H
2
3
1
3
3
(
OCH CH ), 26.7 (C(CH ) ), 27.2 (CH CO), 37.2 (CH Ph), 61.7
2 3 3 3 3 2
(
OCH CH ), 81.2 (C(CH ) ), 92.7 (CH C), 126.8, 128.0, 130.7,
2 3 3 3 2
and Bu NI (0.15 g, 0.40 mmol) was added. The solution was
4
1
35.0 (Ph), 167.7, 203.7 (CO).
Ethyl 2-acetyl-2-(tert-butylperoxy)-5-oxohexanoate 4d
refluxed for 6 hours. A product 10 was isolated as described for
2d. Yield of 10 is (0.49 g, 1.84 mmol, 92 %).
[
7b]
:
1
Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.21 (s, 9H,
[16]
3
9-(tert-Butylperoxy)-9-methyl-9H-fluorene 10: Colorless
(
CH ) C), 1.22 (t, J = 7.2 Hz, 3H, OCH CH ), 2.08 (s, 3H,
1
3
3
H-H
2
3
oil. H NMR (300.15 MHz, CDCl ): δ = 1.16 (s, 9H, (CH ) C),
3
3 3
CH CO), 2.19 (s, 3H, CH CO), 2.30-2.49 (m, 4H, CH CH ), 4.15
13
3
3
2
2
1
3
1.83 (s, 3H, CH
3
), 7.31-7.68 (m, 8H, Ar). С NMR (75.48 MHz,
(q, JH-H = 7.2 Hz, 2H, OCH CH ). C NMR (75.48 MHz,
2 3
CDCl ): δ = 22.5 (CH ), 26.6 (C(CH ) ), 79.5 (C(CH ) ), 87.9
3
3
3 3
3 3
CDCl ): δ = 14.0 (OCH CH ), 25.0 (CH CO), 26.4 (C(CH ) ),
3
2
3
3
3 3
(
CH C), 119.9, 124.9, 127.5, 129.0, 140.0, 146.8 (Ar). Calculated
3
2
9.8, 32.9, 37.3 (CH CO, CH CH ), 61.8 (OCH CH ), 80.9
3 2 2 2 3
for C H O : % C 80.56; % H 7.51; found: % C 80.44; % H
1
8
20
2
(
C(CH ) ), 91.0 (CH C), 167.1, 202.5, 207.4 (CO).
3 3 2
7
.62. HRMS-ESI: calculated 307.1095 [C H O +K] found
18 20 2
1
Ethyl 2-cyanohexanoate 6a: Colorless oil. H NMR (300.15
MHz, CDCl ): δ = 0.90 (t, J = 6.9 Hz, 3H, CH (CH ) ), 1.24-
307.1094 (Δ = 0.3 ppm). IR (film): 2976 (s), 1450 (s), 1363 (s),
1330 (m), 1246 (m), 1212 (m), 1196 (s), 1122 (m), 1096 (m), 877
3
H-H
3
2 3
-
1
1
4
.40 (m, 7H, CH CH , OCH CH ), 1.89-2.00 (m, 2H, CH C),
.31 (q, JH-H = 7.2 Hz, 2H, OCH CH ). C NMR (75.48 MHz,
(m), 761 (vs, υCH Ar), 735 (vs, υCH Ar) cm .
2
2
2
3
2
1
3
2
3
Additional experiment on Bu NI isolation after
4
CDCl ): δ = 13.7 (CH ), 14.1 (OCH CH ), 22.3, 25.8, 35.1 (CH ),
3
3
2
3
2
peroxidation. To a solution of diethyl benzylmalonate 1d (0.50
g, 2.00 mmol) in acetonitrile (10 mL) 70% t-BuOOH (0.77 g,
.00 mmol) was added. The mixture was heated to reflux, and
2
6.4 (C(CH ) ), 63.1 (OCH CH ), 82.3 (C(CH ) ), 82.6 (CH C),
3 3 2 3 3 3 2
1
16.6 (CN), 165.9 (CO). Calculated for C H NO : % C 60.68;
13 23 4
6
%
H 9.01; % N 5.44 found: % C 60.59; % H 8.98; % N 5.54.
then Bu NI (0.15 g, 0.40 mmol) was added. The solution was
4
HRMS-ESI: calculated 280.1519 [C H O +Na] found 280.1525
1
3
23
4
-
1
refluxed for 6 h. The solvent was removed under water aspirator
(Δ = 2.1 ppm). IR (film): 2245 (w, υCN), 1753 (vs, υCO) cm .
pressure. The suspension that formed was diluted with Et O (20
2
Ethyl
2-(tert-butylperoxy)-2-cyano-3-phenylpropanoate
mL), the precipitate was filtered of, washed with Et O (20 mL),
2
[
7a]
1
1
6
b
: Colorless oil. H NMR (300.15 MHz, CDCl ): δ = 1.21 (t,
and collected. Yield of Bu NI is (0.11 g, 0.30 mmol, 75 %). H
3
4
JH-H = 7.2 Hz, 3H, OCH CH ), 1.25 (s, 9H, (CH ) C), 3.22 (d, J
NMR (300.15 MHz, CDCl ): δ = 0.91 (t, 12H, CH , J = 7.2
2
3
3 3
H-
3
3
H-H
=
13.6 Hz, 1H, CH Ph), 3.29 (d, J = 13.6 Hz, 1H, CH Ph),
Hz), 1.28-1.68 (m, 16H, CH CH CH CH ), 3.21-3.35 (m, 8H,
3 2 2 2
13
H
2
H-H
2
4
.24 (q, JH-H = 7.2 Hz, 2H, OCH CH ), 7.20-7.40 (m, 5H, Ph).
C NMR (75.48 MHz, CDCl ): δ = 14.0 (OCH CH ), 26.4
CH N). С NMR (75.48 MHz, CDCl ): δ = 13.8 (CH ), 19.8,
2 3 3
2
3
1
3
24.3 (CH ), 59.2 (CH N). Calculated for C H IN: % C 52.03; %
3
2
3
2 2 16 36
(
C(CH ) ), 41.3 (CH Ph), 63.2 (OCH CH ), 82.6 (C(CH ) ), 82.9
H 9.82; % N 3.79; % I 34.36; found: % C 52.44; % H 9.88; % N
3.71; % I 33.58.
3
3
2
2
3
3 3
(CH C), 116.2 (CN), 128.3, 128.7, 130.5, 131.3, 133.5 (Ph),
2
1
65.3 (CO).

6
Tetrahedron
ACCEPTED MANUSCRIPT
Explosives, Pyrotechnics. 2011, 36, 219-224; e) Östmark, H.;
Wallin, S.; Ang, H. G. Propellants, Explosives, Pyrotechnics.
012, 37, 12-23.
2
Acknowledgment
[
7] a) Terent’ev, A. O.; Borisov, D. A.; Semenov, V. V.; Chernyshev,
V. V.; Dembitsky, V. M.; Nikishin, G. I. Synthesis, 2011, 2091-
2100; b) Terent’ev, A. O.; Borisov, D. A.; Yaremenko, I. A.;
Chernyshev, V. V.; Nikishin, G. I. J. Org. Chem., 2010, 75, 5065-
This study was financially supported by the Russian Science
Foundation (Grant 14-23-00150).
5
071; c) Yaremenko, I. A.; Terent'ev, A. O.; Vil', V. A.; Novikov,
R. A.; Chernyshev, V. V.; Tafeenko, V. A.; Levitsky, D. O.;
Fleury, F.; Nikishin, G. I. Chem. Eur. J., 2014, 20, 10160-10169;
d) Terent'ev, A. O.; Yaremenko, I. A. ; Vil’, V. A.; Моisееv, I. K.;
Kon’kov, S. A.; Dembitsky, V. M.; Levitsky, D. O.; Nikishin, G.
I. Org. Biomol. Chem., 2013, 11, 2613-2623; e) Terent'ev, A. O.;
Yaremenko, I. A.; Vil’, V. A.; Dembitsky, V. M.; Nikishin, G. I.
Synthesis, 2013, 45, 246-250.
Notes and references
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[
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ACCEPTED MANUSCRIPT
Organocatalytic peroxidation
of malonates, β-ketoesters, and cyanoacetic esters
3
using n-Bu NI / t-BuOOH-mediated intermolecular oxidative C(sp )–O coupling
4
a
a
Alexander O. Terent’ev,* Alexander T. Zdvizhkov,
b
b
Dmitri O. Levitsky, Fabrice Fleury,
a
a
a
Roman A. Pototskiy, Alena N. Kulakova, Gennady I. Nikishin
a
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47,
Moscow, 119991, Russian Federation
b
UFIP CNRS UMR 6286, Mechanism and regulation of DNA repair team Université de Nantes,
2
rue de la Houssinière, 44322, France
E-mail: alterex@yandex.ru
1

ACCEPTED MANUSCRIPT
Table of contents
1
1
H NMR of Diethyl (tert-butylperoxy)(methyl)malonate 2a ....................................................................... 5
3
C NMR of Diethyl (tert-butylperoxy)(methyl)malonate 2a ...................................................................... 6
HRMS of Diethyl (tert-butylperoxy)(methyl)malonate 2a .......................................................................... 7
IR of Diethyl (tert-butylperoxy)(methyl)malonate 2a.................................................................................. 8
1
H NMR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b .......................................................................... 9
13
C NMR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b ....................................................................... 10
HRMS of Diethyl (tert-butylperoxy)(ethyl)malonate 2b ........................................................................... 11
IR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b................................................................................... 12
1
H NMR of Diethyl butyl(tert-butylperoxy)malonate 2c ........................................................................... 13
13
C NMR of Diethyl butyl(tert-butylperoxy)malonate 2c .......................................................................... 14
HRMS of Diethyl butyl(tert-butylperoxy)malonate 2c.............................................................................. 15
IR of Diethyl butyl(tert-butylperoxy)malonate 2c ..................................................................................... 16
1
H NMR of Diethyl benzyl(tert-butylperoxy)malonate 2d ........................................................................ 17
1
1
1
1
1
3
С NMR of Diethyl benzyl(tert-butylperoxy)malonate 2d ....................................................................... 18
H NMR of Diethyl allyl(tert-butylperoxy)malonate 2e ............................................................................ 19
3
C NMR of Diethyl allyl(tert-butylperoxy)malonate 2e ........................................................................... 20
H NMR of Diethyl (tert-butylperoxy)(phenyl)malonate 2f ...................................................................... 21
3
C NMR of Diethyl (tert-butylperoxy)(phenyl)malonate 2f ..................................................................... 22
HRMS of Diethyl (tert-butylperoxy)(phenyl)malonate 2f ......................................................................... 23
IR of Diethyl (tert-butylperoxy)(phenyl)malonate 2f................................................................................. 24
1
H NMR of Diethyl (tert-butylperoxy)(3-oxobutyl)malonate 2g............................................................... 25
13
C NMR of Diethyl (tert-butylperoxy)(3-oxobutyl)malonate 2g.............................................................. 26
2

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1
1
1
1
H NMR of Diethyl (tert-butylperoxy)(2-cyanoethyl)malonate 2h............................................................ 27
3
C NMR of Diethyl (tert-butylperoxy)(2-cyanoethyl)malonate 2h .......................................................... 28
H NMR of Ethyl 2-(tert-butylperoxy)-2-methyl-3-oxobutanoate 4a........................................................ 29
3
C NMR of Ethyl 2-(tert-butylperoxy)-2-methyl-3-oxobutanoate 4a....................................................... 30
HRMS of Ethyl 2-(tert-butylperoxy)-2-methyl-3-oxobutanoate 4a........................................................... 31
IR of Ethyl 2-(tert-butylperoxy)-2-methyl-3-oxobutanoate 4a .................................................................. 32
1
H NMR of Ethyl 2-acetyl-2-(tert-butylperoxy)hexanoate 4b ................................................................... 33
1
1
1
1
1
1
1
3
C NMR of Ethyl 2-acetyl-2-(tert-butylperoxy)hexanoate 4b.................................................................. 34
H NMR of Ethyl 2-benzyl-2-(tert-butylperoxy)-3-oxobutanoate 4c......................................................... 35
3
C NMR of Ethyl 2-benzyl-2-(tert-butylperoxy)-3-oxobutanoate 4c........................................................ 36
H NMR of Ethyl 2-acetyl-2-(tert-butylperoxy)-5-oxohexanoate 4d......................................................... 37
3
C NMR of Ethyl 2-acetyl-2-(tert-butylperoxy)-5-oxohexanoate 4d........................................................ 38
H NMR of Ethyl 2-(tert-butylperoxy)-2-cyanohexanoate 6a.................................................................... 39
3
C NMR of Ethyl 2-(tert-butylperoxy)-2-cyanohexanoate 6a .................................................................. 40
HRMS of Ethyl 2-(tert-butylperoxy)-2-cyanohexanoate 6a ...................................................................... 41
IR of Ethyl 2-(tert-butylperoxy)-2-cyanohexanoate 6a.............................................................................. 42
1
H NMR of Ethyl 2-(tert-butylperoxy)-2-cyano-3-phenylpropanoate 6b .................................................. 43
1
1
1
1
1
1
1
3
C NMR of Ethyl 2-(tert-butylperoxy)-2-cyano-3-phenylpropanoate 6b................................................. 44
H NMR of Ethyl 2-(tert-butylperoxy)-2-cyanopent-4-enoate 6c.............................................................. 45
3
C NMR of Ethyl 2-(tert-butylperoxy)-2-cyanopent-4-enoate 6c............................................................. 46
H NMR of Diethyl 2-(tert-butylperoxy)-2-cyanopentanedioate 6d.......................................................... 47
3
C NMR of Diethyl 2-(tert-butylperoxy)-2-cyanopentanedioate 6d......................................................... 48
H NMR of tert-Butyl 9-methyl-9H-fluoren-9-yl peroxide........................................................................ 49
3
C NMR of tert-Butyl 9-methyl-9H-fluoren-9-yl peroxide....................................................................... 50
3

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HRMS of tert-Butyl 9-methyl-9H-fluoren-9-yl peroxide........................................................................... 51
1
H NMR of Tetraethyl ethene-1,1,2,2-tetracarboxylate 3 .......................................................................... 52
13
C NMR of Tetraethyl ethene-1,1,2,2-tetracarboxylate 3 ......................................................................... 53
HRMS of Tetraethyl ethene-1,1,2,2-tetracarboxylate 3 ............................................................................. 54
1
H NMR of tetrabuthylammonium iodide.................................................................................................. 55
13
C NMR of tetrabuthylammonium iodide................................................................................................. 56
4

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H NMR of Diethyl (tert-butylperoxy)(methyl)malonate 2a
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C NMR of Diethyl (tert-butylperoxy)(methyl)malonate 2a
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HRMS of Diethyl (tert-butylperoxy)(methyl)malonate 2a
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IR of Diethyl (tert-butylperoxy)(methyl)malonate 2a
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H NMR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b
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C NMR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b
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HRMS of Diethyl (tert-butylperoxy)(ethyl)malonate 2b
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IR of Diethyl (tert-butylperoxy)(ethyl)malonate 2b
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H NMR of Diethyl butyl(tert-butylperoxy)malonate 2c
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C NMR of Diethyl butyl(tert-butylperoxy)malonate 2c
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HRMS of Diethyl butyl(tert-butylperoxy)malonate 2c
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IR of Diethyl butyl(tert-butylperoxy)malonate 2c
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H NMR of Diethyl benzyl(tert-butylperoxy)malonate 2d
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С NMR of Diethyl benzyl(tert-butylperoxy)malonate 2d
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H NMR of Diethyl allyl(tert-butylperoxy)malonate 2e
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C NMR of Diethyl allyl(tert-butylperoxy)malonate 2e
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H NMR of Diethyl (tert-butylperoxy)(phenyl)malonate 2f
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C NMR of Diethyl (tert-butylperoxy)(phenyl)malonate 2f
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2