Pd-catalyzed allylation of CH acids under phase-transfer conditions

Article abstract of DOI:10.1007/s11172-010-0120-5

The composition of the products obtained by Pd-catalyzed allylation of diethyl (alkyl)- malonates and ethyl cyanoacetate with allylic acetates under phase-transfer conditions using potassium carbonate or phosphate as bases depended strongly on the nature of the reactants and the ligands used. The highest yields and the fraction of the "linear" regioisomers were achieved in the reactions of prenyl or 3-methylbut-1-en-3-yl acetates in the presence of phosphordiamidite ligands.

Full text of DOI:10.1007/s11172-010-0120-5

Russian Chemical Bulletin, International Edition, Vol. 59, No. 3, pp. 605—610, March, 2010
605
Pdꢀcatalyzed allylation of CH acids under phaseꢀtransfer conditions
A. A. Vasil´ev,a S. E. Lyubimov,b E. P. Serebryakov,a V. A. Davankov,b M. I. Struchkova,a and S. G. Zlotina
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: vasiliev@ioc.ac.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5508. Eꢀmail: lssp452@mail.ru
The composition of the products obtained by Pdꢀcatalyzed allylation of diethyl (alkyl)ꢀ
malonates and ethyl cyanoacetate with allylic acetates under phaseꢀtransfer conditions using
potassium carbonate or phosphate as bases depended strongly on the nature of the reactants
and the ligands used. The highest yields and the fraction of the "linear" regioisomers were
achieved in the reactions of prenyl or 3ꢀmethylbutꢀ1ꢀenꢀ3ꢀyl acetates in the presence of
phosphordiamidite ligands.
Key words: allylation, CH acids, Pd complexes, crossꢀcoupling, phosphordiamidites, ligands,
phaseꢀtransfer conditions, Tsuji—Trost reaction.
The Pdꢀcatalyzed reaction of stabilized anions of CH
acids with allylic carboxylates (the Tsuji—Trost reaction)
is a good alternative for the application of allylic halides
and was employed in the synthesis of practically useful
substances.1 The need of preliminary conversion of the
starting CH acid into the carbanion using strong bases
such as NaH, LDA, or a system N,Oꢀbis(trimethylꢀ
silyl)acetamide—potassium acetate is the main disadvanꢀ
tage of this method, which places serious restrictions to its
wide application. In the midꢀ1980s, Russian researchers
showed that the extension of the phaseꢀtransfer concept
on the Tsuji—Trost reaction allowed allylation of several
CH and NH acids to proceed using such inexpensive safe
bases as alkali metal carbonates and hydroxides.2 Since
then, only scarce examples of the use of alkali carbonates
for the deprotonation of CH acids aimed at asymmetric
addition to 3ꢀacetoxyꢀ1,3ꢀdiphenylpropꢀ1ꢀene have been
documented.3 An interesting recent development is allylaꢀ
tion in the presence of R2NLi generated in situ from lithium
metal and a secondary amine with αꢀmethylstyrene as
a hydrogen acceptor.4,5
were obtained from the latter.2a In the present work, the
results of allylation of malonates and cyanoacetates with
allylic acetates using potassium carbonate or phosphate as
the bases are summarized.
Allylation of diethyl malonate (1) with very reactive
allyl acetate (2a) (Scheme 1, Table 1, cf. Ref. 2a) in the
presence of a Pd(dba)2—PPh3 catalytic system (dba is
dibenzylideneacetone) and K2CO3 in toluene proceeded
even without a phaseꢀtransfer catalyst (PTC) (see Table 1,
entry 1) giving the monoallylation product 3a in high yield.
With potassium phosphate, which is better soluble in toluꢀ
ene, the formation of diallylation product 4a was also obꢀ
served (see Table 1, entry 2). Mixtures of both products
were obtained with K2CO3 and quaternary ammonium
salts as PTC (see Table 1, entries 3—5). It is of note that
diallylation product 4a formed exclusively in the presence
of a K2CO3—Bu4NBr system in CH2Cl2 (see Table 1,
entry 6). No PTC is required for the reactions carried out
in aprotic polar solvents, for example, DMF and DMSO
(see Table 1, entries 7 and 8). This allowed us to someꢀ
what simplify the synthetic procedure.
Recently6 we have published preliminary results of sucꢀ
cessful Pdꢀcatalyzed prenylation of diethyl malonate
with prenyl and 3ꢀmethylbutꢀ1ꢀenꢀ3ꢀyl acetates (C5ꢀsynꢀ
thons) under phaseꢀtransfer conditions in the presence of
potassium carbonate with a good regioselectivity provided
by a phosphordiamidite ligand. It should be noted that the
Tsuji—Trost reaction1 is routinely studied with C5ꢀsynꢀ
thons as the linear terpenoind analogs, for example, neryl
acetate (Zꢀ3,7ꢀdimethyloctaꢀ2,6ꢀdienyl acetate). Under
conditions of phaseꢀtransfer catalysis, no target products
Nearly quantitative yields of the diallylation products
were obtained with tributylphosphine as a ligand (see
Table 1, entry 9). Surprisingly, the electronꢀrich sterically
hindered phosphines (tricyclohexylphosphine PCy3 and
SꢀPHOS) were less applicable for our goal (see Table 1,
entries 10 and 11), which is probably due to the strong
shielding of the palladium atom in the activated complex.
Finally, the catalytic systems on the base of recently
synthesized phosphite (L1) and phosphoramidite (L2)
ligands7 were found ineffective (see Table 1, entries
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 592—597, March, 2010.
1066ꢀ5285/10/5903ꢀ0605 © 2010 Springer Science+Business Media, Inc.

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Vasil´ev et al.
Table 1. Reaction of diethyl malonate (1) with allyl acetate (2a)a
12 and 13), while phosphordiamidite (L3) provided the
quantitative yield of diallylation product 4a (see Table 1,
entry 14).
Entry Solꢀ
vent
PTC
Ligand
GS data
Conversion of 1 (%) 3a : 4a
Scheme 1
1
2
3
4
5
6
7
8
Toluene
—
—
PPh3
PPh3
98
100
100
100
100
100
100
100
100
—
100 : 0
Tolueneb
049 : 51
045 : 55
073 : 27
011 : 89
00 : 100
023 : 77
00 : 100
001 : 99
00—0
Toluene BnEt3NCl PPh3
Toluene Bu4NBF4 PPh3
Toluene Bu4NBr PPh3
CH2Cl2 Bu4NBr PPh3
DMF
DMSO
DMF
DMF
DMF
DMF
DMF
DMF
—
—
—
—
—
—
—
—
PPh3
PPh3
PBu3
PCy3
SꢀPHOS
L1
9
10
11
12
13
14
85
—
6
100
0093 : 7
00—0
100 : 0
L2
L3
00 : 100
a Conditions: 2.4 equiv. AllOAc, 3 equiv. K2CO3, 2 mol.% Pd(dba)2,
8 mol.% phosphine or 4 mol.% phosphordiamidite, 10 mol.%
PTC, 20 °C, 18 h.
b K3PO4 was used as a base.
Based on these data, we studied prenylation of diethyl
malonate (1) with 3ꢀmethylbutꢀ1ꢀenꢀ3ꢀyl acetate (2b) and
its isomer, prenyl acetate, (2b´). The isomers 2b and 2b´
usually produce a similar set of the products because they
generate the same πꢀallyl complex in the catalytic cycle
(Scheme 2, cf. Ref. 8). In the case of tertiary acetate 2b, no
variations in the phosphine ligands provides the high fracꢀ
tion of "linear" isomer 3b (Table 2, entries 1—6) (cf. Ref. 9).
Scheme 2
The fraction of isomer 3b reached 77% with the use of
phosphordiamidite ligands L3—L6 (see Table 2, entries
7—12) with nearly complete conversion of the starting
CH acid 1. In the case of sterically more hindered ligand
L7 and bidentate ligand L8, the fraction of the "linear" isoꢀ
mer (see Table 2, entries 13 and 14) decreased noticeably.
Reagents and condition: 2a, Pd(dba)2, ligand, base, solvent, PTC,
20 °C, 18 h (see Table 1).

Palladiumꢀcatalyzed allylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
607
a
Table 2. Reaction of diethyl malonate (1) with allylic acetates 2b and 2b´
Entry
Allylic
acetate
Solvent
PTC
Ligand
GC data
Conversion of 1 (%) 3b : 3b´
1
2
3
4
5
6
7
8
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
2b
DMF
CH2Cl2
DMF
CH2Cl2
DMF
DMF
DMF
DMSOb
DMF
DMF
CH2Cl2
DMF
DMF
DMF
DMF
DMF
DMSO
DMF
DMF
DMF
DMF
—
Bu4NBr
—
Bu4NBr
PPh3
PPh3
PBu3
PBu3
PCy3
SꢀPHOS
L3
100
53
76
81
—
44
100
100
100
98
98
97
84
83
—
57
98
—
—
18
94
16 : 84
06 : 94
44 : 56
17 : 83
—
48 : 52
77 : 23
68 : 32
77 : 23
77 : 23
69 : 31
67 : 33
26 : 74
40 : 60
—
40 : 60
43 : 57
—
—
77 : 23
71 : 29
—
—
—
—
—
L3
L4
L5
L5
L6
L7
L8
9
10
11
12
13
14
15
16
17
18
19
20
21
—
Bu4NBr
—
—
—
—
—
—
—
—
—
2b
2b´
2b´
2b´
2b´
2b´
2b´
2b´
PPh3
PBu3
PBu3
PCy3
SꢀPHOS
L3
—
L4
a Conditions: 1.5 equiv. 2b or 2b´, 2 eqiuv. K2CO3, 2 mol.% Pd(dba)2, 8 mol.% phosphine or 4 mol.% phosphorꢀ
diamidite, 10 mol.% PTC, 20 °C, 18 h.
b Yields in N,Nꢀdimethylacetamide and Nꢀmethylpyrrolidone are ~90%, in N,N´ꢀdimethylpropyleneurea
(DMPU) is 64% (3b : 3b´ ≈ 70 : 30), in HMPA no reaction was observed.
The use of prenyl acetate 2b´ led to a decrease in the
product yields (see Table 2, entries 15—21). This fact could
be explained by slower coordination of palladium with the
sterically less accessible trisubstituted double bond of 2b´
as compared with 2b. The close ratios of "linear" and
"branched" isomers 3b/3b´ obtained under similar reacꢀ
tion conditions deserve attention (cf. entries 3 and 16, 7
and 20, 9 and 21). This fact indicated that the "allylic
carboxylate memory effect", which is common for the fulꢀ
ly deprotonated CH acids,8 is not observed. Probably,
K2CO3 provided low concentration of the carbanion which
in turn decreases the rate of the reaction of the carbanion
with the second reaction species. Probably, this species,
which also has low quasiꢀsteadyꢀstate concentration, is
the resulting πꢀallyl organopalladium complex (identical
for both allylic acetates 2b and 2b´) rather than its precurꢀ
sors (different for 2b and 2b´), which can also react with
carbanions.
Reaction of crotyl acetate 2c and its isomer 2c´ with an
excess of diethyl malonate (1) afforded a mixture of isoꢀ
Scheme 3
Reagents and conditions: i. 1 (1.5 equiv.), Pd(dba)2, ligand, K2CO3, DMF, 20 °C; ii. the same with starting ratio 1 : 2c (or 2c´) = 1 : 4.

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Vasil´ev et al.
meric monosubstitution products 3c and 3c´ (Scheme 3).
The isomer ratio depended on the nature of the ligand.
Ligands PPh3, L3, and L8 afforded isomers 3c and 3c´ in
~2 : 3, ~3 : 2, and 2 : 1 ratios, respectively. With the excess
of substrates 2c or 2c´, the subsequent allylation proceedꢀ
ed readily to give compounds 4b and 4b´.
The data for allylation of the Cꢀsubstituted malonates
5 and 6 are summarized in Scheme 4 and in Table 3. The
reaction of methylꢀsubstituted derivative 5 with allyl acꢀ
etate (2a) proceeded smoothly, while in the case of
3ꢀmethylbutꢀ1ꢀenꢀ3ꢀyl acetate (2b) the high yield of prodꢀ
uct 9 was achieved only in the presence of phosphordiꢀ
amidite ligand L4 (see Table 3, entry 6). It is of note that no
formation of a "branched" isomer, homolog of compound
3b´, was observed under these conditions. The reactions of
sterically more hindered diethyl cyclohexylmalonate (6)
with unsubstituted allyl acetate (2a) furnished compound
8 in yields from low to moderate (entries 7—10). Thereꢀ
fore, attempts to prenylate malonate 6 with either 2b or
2b´ failed.
ied. With the excess of reactive allyl acetate (2a), the
initially formed allylation product 11 underwent readꢀ
ily additional allylation (Scheme 5, Table 4, entries 1
and 2). Prenylation of compound 10 with 2b in the
presence of phosphines yielded exclusively "branched"
product 13´ (see Table 4, entries 3 and 4), while phosꢀ
phordiamidite L3 provided some "linear" isomer 13 (see
Table 4, entry 5). It is of note that in this experiꢀ
ment the excess of ethyl cyanoacetate (10) has to be used
otherwise product 13 underwent readily additional preꢀ
nylation.
Scheme 5
Scheme 4
i. Pd(dba)2, ligand, K2CO3, DMF 20 °C.
R = Me (5, 7), Cy (6, 8)
In summary, we have demonstrated that Pdꢀcatalyzed
allylation and, in particular, prenylation, of the CH acids
could successfully be carried out using K2CO3 as a base.
Phosphordiamidite ligands favored the formation of "linꢀ
ear" isomers. The obtained results opened the prospects
for the development of convenient methods toward funcꢀ
tionalized unsaturated compounds, for example, terpeꢀ
noids of practical value.1,11
Allylation of ethyl cyanoacetate (10), which is a stronꢀ
ger CH acid (pKa ~13) than diethyl malonate (1)
(pKa ~15)10 and hence is less nucleophilic, was also studꢀ
Table 3. Allylation of malonates 5 and 6
Entry
R
CH
acid acetatea
Allylic Ligand Solvent Proꢀ Yieldb
duct (%)
1
2
3
4
5
6
7
8
9
10
Me
Me
Me
Me
Me
Me
Cy
Cy
Cy
Cy
5
5
5
5
5
5
6
6
6
6
2a
2b
2b
2b
2b
2b
2a
2a
2a
2a
PPh3
PPh3
PBu3
PBu3
L3
DMF
DMF
DMF
DMSO
DMSO
DMSO
DMF
DMF
DMF
DMSO
7
9
9
9
9
9
8
8
8
8
100
0
0
36
23
94
51
27
5
Table 4. Allylation of ethyl cyanoacetate (10)
Entry
Allylic acetate
Ligand
Product
Yielda (%)
L4
1
2
3
4
5
2a (0.5 equiv.)
2a (2.5 equiv.)
2b (2.5 equiv.)
2b (2.5 equiv.)
2b (0.5 equiv.)
PPh3
PPh3
PPh3
PBu3
L3
11
12
13´
13´
13+13´
100b
100
37
100
31+69b
PPh3
PBu3
L3
L3
19
a 1.5 equiv. 2а or 2b was used.
b The yield is taken to be equal to the conversion of the starting
CH acids determined by GC.
a The yield is taken to be equal to the conversion of compound
10 determined by GC.
b The same, with account of the excess of compound 10.

Palladiumꢀcatalyzed allylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 3, March, 2010
609
and concentrated in vacuo, followed by column chromatography
of the residue (SiO2, eluent — gradient of EtOAc in petroleum
ether, 0→5%). No separation of the resulting "linear" and
"branched" isomers by column chromatography occurred. Howꢀ
ever, monoꢀ and diallylation products and the starting CH acids
exhibited different Rf on TLC. Diethyl allyl(cyclohexyl)malonꢀ
ate (8)18 was identified by GC/MS (m/z: 282 [M]+).
Experimental
The 1H and 13C NMR spectra were recorded on a Bruker
AMꢀ300 spectrometer in CDCl3 at 300.13 and 75.47 MHz, reꢀ
spectively. Chemical shifts are given in the δ scale relative to
a signal of the residual protons (1H) or a signal of a deuteratꢀ
ed solvent (13C). The chromatomass spectrometry was perꢀ
formed on an Agilent Technologies 85973 Network (EI, 70 eV)
mass spectrometer coupled with an Agilent Technologies 6890
chromatograph, which was equipped with a capillary column
(HPꢀ5MS 30000×0.25 mm), the temperature of injector and
flame ionization detector was 280 °C, the thermostat temperaꢀ
ture was programmed as follows: 60 (5 min), then 60→300 °C
Diethyl allylmalonate (3a). 1H NMR, δ: 1.24 (t, 6 H, J = 7.0 Hz);
2.61 (t, 2 H, J = 7.0 Hz); 3.39 (t, 1 H, J = 7.4 Hz); 4.17 (q, 4 H,
J = 7.0 Hz); 5.03 (d, 1 H, J = 11.3 Hz); 5.09 (d, 1 H, J = 17.7 Hz);
5.76 (m, 1 H). The product is identical to the authentic sample.
1
Diethyl diallylmalonate (4a), colorless oil. H NMR, δ: 1.23
(t, 6 H, J = 7.3 Hz); 2.62 (d, 4 H, J = 7.3 Hz); 4.17 (q, 4 H,
J = 7.3 Hz); 5.08 (d, 1 H, J = 11.2 Hz); 5.09 (d, 1 H, J = 16.1 Hz);
5.65 (m, 1 H). The spectral data of 4a are in good agreement
with the published data.19
10 deg min–1, flow rate of the carrier gas (helium) was 2 mL min–1
.
During the analysis, the total ion current and the signal of
the flame ionization detector were registered in parallel. The
GC analysis was carried out on a Chromꢀ5 chromatograph (the
injector and detector temperature was 270 °C) on a column
(2×2500 mm) with SEꢀ30 on Chromaton NꢀAWꢀDMCS (the
thermostat temperature of 150—180 °C depending on the nature
of the sample) or a capillary column (0.2×25000 mm) with SEꢀ30
(the thermostat temperature was programmed as follows:
120→230 °C, 10—15 deg min–1). The composition of the mixꢀ
tures was calculated using a normalization method.
Commercially available CH acids 1, 5, and 10; allylic aceꢀ
tates 2a and 2b´; quaternary ammonium salts and phosphines
(PPh3 and PBu3) (Aldrich) were used. Diethyl cyclohexylmaꢀ
lonate (6), which was synthesized by the known procedure,12
was a kind gift from G. M. Zhdankina and G. V. Kryshtal. Allylꢀ
ic acetates 2c and 2c´ were synthesized by acylation of the correꢀ
sponding alcohols with acetic anhydride in the presence of
DMAP by the standard procedure. 3ꢀMethylbutꢀ1ꢀenꢀ3ꢀyl
acetate (2b) was obtained by acylation of 3ꢀmethylbutꢀ1ꢀenꢀ3ꢀol
with acetic anhydride in CH2Cl2 in the presence of NEt3 and
DMAP as described.13 Potassium carbonate (Reakhim, USSR)
was calcined in air, kept in a closed vessel, and ground in a mortar
prior to use. Potassium phosphate (granulated, Aldrich) was
ground in a mortar prior to use. Bis(dibenzylideneacetone)ꢀ
palladium (Pd(dba)2)14 and SꢀPHOS15 were synthesized by the
known methods. Ligands L1—L8 were obtained by the known
procedures,16,17 their physicochemical properties were described
previously.6,7a,b,d The solvents were distilled prior to use.
Allylation of CH acids (general procedure). A CH acid
(0.5 mmol), a solvent (1 mL), and PTC (0.05 mmol, if required)
were placed in a Schlenk tube equipped with magnetic stirring
bar and a rubber septum. The mixture was deaerated three times
by evacuation and refilling with argon (in the case of CH2Cl2,
evacuation was carried out with care, boiling of the solvent being
controlled). The catalyst, Pd(dba)2 (6 mg, 0.01 mmol), and
a ligand (0.04 mmol) were added, and the mixture was stirred
until the color changed from darkꢀred to yellow. To a stirred
mixture, an allylic acetate (1.25 mmol in the case of CH acids 1
and 10 and 0.75 mmol in the case of CH acids 5 and 6) was
added. After 10 min, potassium carbonate (2 mmol in the case of
CH acids 1 and 10 and 1 mmol in the case of CH acids 5 and 6)
was added. Each opening of the Schlenk tube was followed by
evacuation and refilling with argon. The mixture was stirred for
18 h at ~20 °C (GC monitoring; in most cases, the reaction
completed in 5—6 h). For the GC analysis, an aliquot was treatꢀ
ed with water and extracted with diethyl ether. The products
were isolated analogously; the extract was dried with Na2SO4
Diethyl (3ꢀmethylbutꢀ2ꢀenꢀ1ꢀyl)malonate (3b) and diethyl
(3ꢀmethylbutꢀ1ꢀenꢀ3ꢀyl)malonate (3b´), colorless oil.
1
Compound 3b. H NMR, δ: 1.24 (t, 6 H, J = 7.0 Hz); 1.62
(s, 3 H); 1.67 (s, 3 H); 2.57 (t, 2 H, J = 7.4 Hz); 3.30 (t, 1 H,
J = 7.7 Hz); 4.17 (q, 4 H, J = 6.6 Hz); 5.06 (br.t, 1 H, J = 7.4 Hz).
The spectral data of 3b are in good agreement with the published
data.8b,18,19 MS (m/z): 228 [M]+.
Compound 3b´. 1H NMR, δ: 1.23 (s, 6 H); 1.24 (t, 6 H,
J = 7.0 Hz); 3.31 (s, 1 H); 4.15 (q, 4 H, J = 6.6 Hz); 4.98 (d, 1 H,
J = 10.3 Hz); 5.01 (d, 1 H, J = 17.7 Hz); 6.05 (dd, 1 H, J = 17.7 Hz,
J = 10.3 Hz). The spectral data of 3b´ are in good agreement
with the published data.8b,20 MS (m/z): 228 [M]+.
Diethyl (butꢀ2ꢀenꢀ1ꢀyl)malonate (3c) and diethyl (butꢀ1ꢀenꢀ
3ꢀyl)malonate (3c´). Unseparable mixture in the ratio of
3c : 3c´ = 2 : 1 were obtained by the reaction of diethyl malonate
(1) (0.75 mmol) and crotyl acetate (0.5 mmol) (2c) (ligand L8),
colorless oil.
Compound 3c (E/Z = 9 : 1). 1H NMR, δ: 1.21 (t, 6 H,
J = 6.9 Hz); 1.58 (d, 3 H, J = 6.2 Hz); 2.51 (t, 1.8 H, J = 7.7 Hz,
=CCH2 Eꢀisomer); 2.59 (t, 0.2 H, J = 7.7 Hz, =CCH2, Zꢀisoꢀ
mer); 3.31 (t, 1 H, J = 7.3 Hz); 4.15 (q, 4 H, J = 6.2 Hz); 5.33
(m, 1 H); 5.48 (m, 1 H). The spectral data of 3c are in good
agreement with the published data.8b,18,19 MS (m/z): 214 [M]+.
Compound 3c´. 1H NMR, δ: 1.05 (d, 3 H, J = 6.7 Hz); 1.19
(t, 3 H, J = 6.9 Hz); 1.22 (t, 3 H, J = 6.9 Hz); 2.89 (m, 1 H); 3.22
(d, 1 H, J = 8.8 Hz); 4.08—4.17 (m, 4 H); 4.96 (d, 1 H, J = 10.3 Hz);
5.04 (d, 1 H, J = 17.2 Hz); 5.73 (m, 1 H). The spectral data of 3c´
are in good agreement with the published data.8b,20 MS (m/z):
214 [M]+.
A mixture of diethyl di(bytꢀ2ꢀenꢀ1ꢀyl)malonate (4b), diethyl
(butꢀ2ꢀenꢀ1ꢀyl)(butꢀ1ꢀenꢀ3ꢀyl)malonate (4b´) and compound (3c´)
(59 : 14 : 27) was obtained by the reaction of diethyl malonate
(1) (0.5 mmol) with crotyl acetate (2c) (2 mmol) in the presence
of ligand L8. Column chromatography afforded the mixture of
compounds 4b and 4b´ in the ratio of 7 : 3, colorless oil.
1
Compound 4b. H NMR, δ: 1.22 (t, 6 H, J = 7.1 Hz); 1.62
(d, 6 H, J = 6.4 Hz); 2.53 (d, 4 H, J = 7.3 Hz); 4.16 (q, 4 H, J =
= 7.1 Hz); 5.26 (m, 2 H); 5.47 (m, 2 H). The spectral data of 4b are
in good agreement with the published data.21 MS (m/z): 268 [M]+.
Compound 4b´. 1H NMR, δ (characteristic signals): 1.09
(d, 3 H, J = 7.3 Hz); 2.60 (d, 3H, J = 7.7 Hz); 2.84 (quint, 1 H,
J = 7.8 Hz); 5.02 (d, 1 H, J = 10.3 Hz); 5.03 (d, 1 H, J = 17.6 Hz);
5.78 (m, 1 H); other signals overlap with the signals of comꢀ
pound 4b. The spectral data of 4b´ are in good agreement with
the published data.22 MS (m/z): 268 [M]+.

610
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Vasil´ev et al.
1
Diethyl allyl(methyl)malonate (7). H NMR, δ: 1.23 (t, 6 H,
5. F. GaudemarꢀBardone, M. Bardone, Synthesis, 1979, 463.
6. A. A. Vasil´ev, S. E. Lyubimov, E. P. Serebryakov, V. A.
Davankov, S. G. Zlotin, Mendeleev Commun., 2009, 103.
7. (a) K. N. Gavrilov, V. N. Tsarev, S. E. Lyubimov, A. A.
Shiryaev, S. V. Zheglov, O. G. Bondarev, V. A. Davankov,
A. A. Kabro, S. K. Moiseev, V. N. Kalinin, Mendeleev Comꢀ
mun., 2003, 134; (b) V. N. Tsarev, S. E. Lyubimov, A. A.
Shiryaev, S. V. Zheglov, O. G. Bondarev, V. A. Davankov,
A. A. Kabro, S. K. Moiseev, V. N. Kalinin, K. N. Gavrilov,
Eur. J. Org. Chem., 2004, 2214; (c) K. N. Gavrilov, V. N.
Tsarev, A. A. Shiryaev, O. G. Bondarev, S. E. Lyubimov,
E. B. Benetsky, A. A. Korlyukov, M. Yu. Antipin, V. A.
Davankov, H.ꢀJ. Gais, Eur. J. Inorg. Chem., 2004, 629;
(d) K. N. Gavrilov, S. V. Zheglov, P. A. Vologzhanin, M. G.
Maksimova, A. S. Safronov, S. E. Lyubimov, V. A. Davanꢀ
kov, B. Schaffner, A. Borner, Tetrahedron Lett., 2008,
49, 3120.
J = 6.8 Hz); 1.37 (s, 3 H); 2.59 (d, 2 H, J = 6.4 Hz); 4.16 (q, 4 H,
J = 6.8 Hz); 5.07 (d, 1 H, J = 10.7 Hz); 5.08 (d, 1 H, J = 16.1 Hz);
5.66 (m, 1 H). The spectral data of 7 are in good agreement with
the published data.23
Diethyl methyl(3ꢀmethylbutꢀ2ꢀenꢀ1ꢀyl)malonate (9). 1H NMR,
δ: 1.24 (t, 6 H, J = 6.8 Hz); 1.37 (s, 3 H); 1.62 (s, 3 H); 1.69
(s, 3 H); 2.58 (d, 2 H, J = 7.3 Hz); 4.17 (q, 4 H, J = 6.8 Hz); 5.01
(m, 1 H). 13C NMR, δ: 13.9 (Me); 17.8 (Me); 19.5 (Me); 25.9
(Me); 33.9 (CH2); 53.8 (C); 61.0 (OCH2); 118.0 (=CH); 135.4
(=C); 172.2 (C=O). The spectral data of 9 are in good agreeꢀ
ment with the published data.24
1
Ethyl 2ꢀcyanopentꢀ4ꢀenoate (11). H NMR, δ: 1.32 (t, 3 H,
J = 7.0 Hz); 2.61—2.69 (m, 2 H); 3.56 (t, 1 H, J = 6.8 Hz); 4.48—4.59
(m, 2 H); 5.17—5.30 (m, 2 H); 5.80 (m, 1 H). The spectral data
of 11 are in good agreement with the published data.19
Ethyl 2ꢀallylꢀ2ꢀcyanopentꢀ4ꢀenoate (12). 1H NMR, δ: 1.30
(t, 3 H, J = 7.0 Hz); 2.48—2.63 (m, 4 H); 4.25 (q, 2 H, J = 7.0 Hz);
5.20—5.28 (m, 4 H); 5.80 (m, 2 H). The spectral data of 12 are in
good agreement with the published data.19
8. (a) T. Cuvigny, M. Julia, C. Rolando, J. Organomet. Chem.,
1985, 285, 395; (b) T. Cuvugny, M. Julia, J. Organomet.
Chem., 1986, 317, 383.
Ethyl 3,3ꢀdimethylꢀ2ꢀcyanopentꢀ4ꢀenoate (13´). 1H NMR,
δ: 1.28 (s, 6 H); 1.30 (t, 3 H, J = 7.3 Hz); 3.36 (s, 1 H); 4.24 (q, 2 H,
J = 6.8 Hz); 5.14 (d, 1 H, J = 17.1 Hz); 5.15 (d, 1 H, J = 10.7 Hz);
5.91 (dd, 1 H, J = 17.6 Hz, J = 10.8 Hz). 13C NMR, δ: 14.0 (Me);
24.5 (Me); 25.2 (Me); 40.0 (C); 48.7 (CH); 62.4 (OCH2); 114.3
(=CH2); 115.6 (CN); 142.2 (=CH); 164.8 (C=O). The spectral
data of 13´ are in good agreement with the published data.8a
Ethyl 5ꢀmethylꢀ2ꢀcyanohexꢀ4ꢀenoate (13) was obtained as
a mixture with isomer 13´ (31 : 69). 1H NMR, δ: 1.31 (d, 3 H,
J = 7.3 Hz); 1.67 (br.s, 3 H); 1.74 (br.s, 3 H); 2.65 (t, 2 H,
J = 6.6 Hz); 3.47 (t, 1 H, J = 6.6 Hz); 4.26 (q, 2 H, J = 6.8 Hz);
5.18 (br.s, 1 H). The spectral data of 13 are in good agreement
with the published data.8a
9. (a) P. G. Andersson, J.ꢀE. Bäckvall, J. Org. Chem., 1991, 56,
5349; (b) Y. I. M. Nilsson, P. G. Andersson, J.ꢀE. Bäckvall,
J. Am. Chem. Soc., 1993, 115, 6609.
10. O. A. Reutov, I. P. Beletskaya, K. P. Butin, CHꢀkisloty
[CH acids], Nauka, Moscow, 1980, 247 pp. (in Russian).
11. E. P. Serebryakov, G. V. Kryshtal, G. M. Zhdankina, A. G.
Nigmatov, V. V. Teplov, L. V. Filatova, Khim.ꢀFarm. Zh.,
2006, 40 [Pharm. Chem. J. (Engl. Transl.), 2006, 40].
12. (a) E. Hope, W. H. Perkin, J. Chem. Soc., 1909, 95, 1360;
(b) N. N. Sukhanov, L. N. Trappel, V. N. Chetverikov, L. A.
Yanovskaya, Zh. Org. Khim., 1985, 21, 2503 [J. Org. Chem.
USSR (Engl. Transl), 1985, 21, 2288].
13. I. D. G. Watson, A. K. Yudin, J. Am. Chem. Soc., 2005,
127, 17516.
This work was financially supported by the Presidium
of the Russian Academy of Sciences (Program "Developꢀ
ment of Synthetic Methods toward Chemical Substances
and Molecular Design of Novel Materials").
14. M. F. Rettig, P. M. Maitlis, Inorg. Synth., 1990, 28, 110.
15. T. E. Barder, S. D. Walker, J. R. Martinelli, S. L. Buchwald,
J. Am. Chem. Soc., 2005, 127, 4685.
16. K. N. Gavrilov, S. E. Lyubimov, S. V. Zheglov, E. B.
Benetsky, V. A. Davankov, J. Mol. Catal. A: Chem., 2005,
231, 255.
17. H. Bernsmann, M. van den Berg, R. Hoen, A. J. Minnaard,
G. Mehler, M. Reetz, J. de Vries, B. Feringa, J. Org. Chem.,
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Received June 8, 2009;
in revised form September 3, 2009