Asymmetric alkene cycloalumination by AlEt3, catalyzed with neomenthylindenyl zirconium η5-complexes

Article abstract of DOI:10.1016/j.jorganchem.2012.10.021

The paper is devoted to a study of the reaction of terminal alkene cycloalumination by AlEt₃ catalyzed with neomenthylindenyl zirconium complexes (p-S)(p-S)-bis[η⁵-[1-[(1S,2S,5R)-2-isopropyl-5- methylcycloh-exyl]indenyl]]zirconium dichloride (1) or (p-S)-(η⁵- cyclopentadienyl)[η⁵-[1-[(1S,2S,5R)-2-isopropyl-5- methylcyclohexyl]indenyl]]zirconium dichloride (2). It was shown that alkene and catalyst structures, as well as solvent, affect the overall yield and enantiomeric excess of the reaction product - 3-alkylsubstituted aluminacyclopentanes. The reaction of terminal alkenes with AlEt₃, catalyzed by complex 1, in hydrocarbon solvents gives predominantly S-enantiomers of cyclic organoaluminum compounds with enantiomeric excess up to 37%. Complex 2 shows smaller stereoinduction effect and provides R-enantiomers of aluminacyclopentanes with 6-26%ee. The effectiveness of selenium-containing derivatizing reagent (R)-2-phenylselenopropanoic acid for the enantiomeric excess estimation in β-alkyl-1,4-butanediols obtained from cyclic organoaluminum compounds was shown.

Full text of DOI:10.1016/j.jorganchem.2012.10.021

Journal of Organometallic Chemistry 723 (2013) 19e25
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Asymmetric alkene cycloalumination by AlEt3, catalyzed with neomenthylindenyl
zirconium
h
5-complexes
*
Lyudmila V. Parfenova , Pavel V. Kovyazin, Tatyana V. Tyumkina, Tatyana V. Berestova,
Leonard M. Khalilov, Usein M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 450075, Ufa, Prospect Oktyabrya, 141, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
The paper is devoted to a study of the reaction of terminal alkene cycloalumination by AlEt3 catalyzed with
neomenthylindenyl zirconium complexes (p-S)(p-S)-bis[
h
5-[1-[(1S,2S,5R)-2-isopropyl-5-methylcycloh-
Received 2 July 2012
Received in revised form
1 September 2012
exyl]indenyl]]zirconium dichloride (1) or (p-S)-( h
h
5-cyclopentadienyl)[ 5-[1-[(1S,2S,5R)-2-isopropyl-5-
methylcyclohexyl]indenyl]]zirconium dichloride (2). It was shown that alkene and catalyst structures, as
well as solvent, affect the overall yield and enantiomeric excess of the reaction product - 3-alkylsubstituted
aluminacyclopentanes. The reaction of terminal alkenes with AlEt3, catalyzed bycomplex 1, in hydrocarbon
solvents gives predominantly S-enantiomers of cyclic organoaluminum compounds with enantiomeric
excess up to 37%. Complex 2 shows smaller stereoinduction effect and provides R-enantiomers of alumi-
nacyclopentanes with 6e26%ee.
Accepted 10 October 2012
Keywords:
Zirconocene complexes
Cycloalumination
b
-Alkyl-1,4-butanediols
The effectiveness of selenium-containing derivatizing reagent (R)-2-phenylselenopropanoic acid for
MTPA
the enantiomeric excess estimation in
compounds was shown.
b
-alkyl-1,4-butanediols obtained from cyclic organoaluminum
(R)-2-phenylselenopropanoic acid
Ó 2012 Elsevier B.V. All rights reserved.
1. Introduction
Earlier, there were attempts to involve enantiopure Ti and Zr
complexes of C1- and C2-symmetry in alkene cycloalumination
[3,4]. Our investigations concerning the reaction of 1-hexene with
AlEt3 in the presence of neomenthyl zirconocene complexes
demonstrated that the enantioselectivity depends on the catalyst
structure and the reaction conditions [4]. The present work is
devoted to a detailed study of asymmetric alkene cycloalumination,
mainly of the substrate structure effect on the chemo- and enan-
tioselectivity of the reaction. Moreover, a new derivatizing reagent
(R)-2-phenylselenopropanoic acid (R-PSPA) has been tested for the
The reaction of AlEt3 with terminal alkenes in the presence of
Cp2ZrCl2, according to the Dzhemilev procedure [1], provides cyclic
organoaluminum compounds (OAC)
which possess immense synthetic potential due to their reactivity
with various electrophilic and nucleophilic reagents providing
wide range of products, for example, 1,4-butanediols, halogen
substituted derivatives, carbo- and hetero-(O, N, S, Se, Si, P) cycles,
etc. [2].
e aluminacyclopentanes,
estimation of the enantiomeric excess of
b-substituted 1,4-
Cp2ZrCl2
Et2Al
butanediols obtained after the oxidation and hydrolysis of the
cyclic OAC.
+
EtAl
-EtH
R
R
2. Results and discussion
The reaction of AlEt3 with terminal alkenes 3aeg in the pres-
ence of 8 mol% of catalysts 1 or 2 at room temperature in hydro-
carbon solvents (hexane, cyclohexane, benzene) provides alumin-
acyclopentanes 4aeg (Scheme 1, Table 1). Carbo- (5aeg) and
hydroalumination products (6aeg) were identified as well.
Asymmetric induction in catalytic alkene cycloalumination
could result in effective methods for the enantioselective synthesis
of practically important
their derivatives.
b-substituted metallacyclopentanes and
The absolute configuration of
nacyclopentanes 4aeg and the enantiomeric excess were estab-
lished by the analysis of the oxidation and hydrolysis products e b-
b-stereogenic centers in alumi-
* Corresponding author.
E-mail address: luda_parfenova@mail.ru (L.V. Parfenova).
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.10.021

20
L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
alkyl-1,4-butanediols 7aeg (Table 1). They were involved in the
reaction with R-MTPA (S-MTPA-Cl) [6] and (R)-2-phenylseleno
propanoic acid [7] (R-PSPA) to yield the corresponding esters 9ae
g and 10aeg.
runs with 70e99% alkene conversion; however, the cyclo-
alumination enantioselectivity is low and does not exceed 17%ee.
The dilution of the reaction media with hydrocarbons dramatically
reduces the alkene conversion to 11e42%; nevertheless, it increases
OMTPA2
OPSPA2
4
Ph
3
2
OH
OH
4
1
R- PSPA
4
1
R- MTPA
CF3
3
2
3
2
SePh
O
(5)
R
1
*
O
*
OMe
*
*
R
R
*
O
7a-g
O
9a-g
10a-g
13C NMR spectra of esters 9bee, substituted with linear alkyl
groups exhibit a double set of signals for C2, C3 and C5 carbon atoms.
More bulky isobutyl (9g) and cyclohexyl (9f) substituents provide
additional diastereomeric signal splitting for C4, C6 and C1 atoms.
The signal splitting for characteristic C2 and C5 in 9beg is in full
the enantiomeric excess of cycloalumination product 4aeg up to
37%ee (for example, entries 1, 2, 5, 8, 11, 13, 14, 18, 21). The reaction
catalyzed with complex 2 runs with decreased alkene conversion
and enantioselectivity of 6e26%ee, which are less sensitive to the
solvent effect.
agreement with the diastereomeric effects in MTPA ester of
butyl-1,4-butanediol (9a) [4]; this leads to conclusions about the
absolute configuration of -stereogenic centers in 7beg.
b
-
The aluminacyclopentanes obtained in the reaction of alkenes
3aeg with AlEt3 in the presence of catalyst 1 were enriched with S-
enantiomers, while the catalysis by complex 2 predominantly gave
R-enantiomers of cyclic OAC. The substituent seniority order
changes in cyclohexyl substituted aluminacyclopentaine 4g,
therefore, the product has the opposite descriptor of the absolute
configuration, however, arrangement of the related atomic groups
b
In 77Se NMR spectra of (R)-phenylselenopropanoic acid esters of
(2R,S)-alkyl-1,4-butanediols (10aeg) two pairs of signals of RRR-
and RRS-diastereomers with DdSe z 0.1e0.3 ppm in the range of
452e454 ppm were observed. The diastereomeric ratios of 10aeg
obtained from 77Se NMR spectra coincided with the ratio of the
corresponding diastereomeric R-MTPA esters 9aeg determined
from the 13C NMR spectra. It should be noted that R-PSPA was more
useful and convenient for the enantiomeric excess elucidation,
at
b
-stereogenic center remains the same as in 4aef.
The length increase for the alkyl chain in the linear alkenes, for
example, using of 1-nonene (3d) or 1-decene (3e) in the reaction,
catalyzed with complex 1, decreases the cycloalumination enan-
tioselectivity to 23e26%ee (entries 11, 13, 14). Moreover, the
involvement of sterically hindered alkenes 4-methylpentene-1 (3f)
or vinylcyclohexane (3g) in the reaction provides cyclic OACs with
reduced enantiomeric excess of 24e25%ee (entries 18, 21). In the
case of catalyst 2 the same effects were observed.
Therefore, the enantioselectivity of the alkene cyclo-
alumination by AlEt3, catalyzed with neomenthyl zirconocene
complexes, is mainly determined by the catalyst structure, the
substrate bulkiness and the solvent nature. In order to explain the
observed effects, a probable mechanism of the process should be
considered. As it was shown previously [8e11], the key
because it readily reacted with
b-substituted 1,4-butanediols,
compared to R-MTPA, in addition to a time-saving during the
measurement of 77Se NMR spectra. In contrast to R-PSPA, the
reaction of S-MTPA-Cl with 7aeg proceeds for w8 h and the yield of
the esters largely depends on the dryness of the initial alcohols.
Moreover, longer accumulation of 13C NMR spectra is required.
As follows from Table 1, the catalyst and substrate structure, as
well as solvent, remarkably affect the alkene conversion and the
reaction chemo- and enantioselectivity. Thus, complex 1 shows
higher activity in the absence or in the reduced amount of the
solvent (for example, entries 3, 4, 7, 10, 12, 15, 20, 22) and reaction
Et
1 or 2
AlEt2
+
+
AlEt3
+
*
AlEt2
R
AlEt
R
*
220C
R
R
6a-g
3a-h
5a-g
4a-g
R= n-C4H9 (a); n-C5H11 (b); n-C6H13 (c);
n-C7H15 (d); n-C8H17 (e); i-C4H9 (f); Cy (g)
O2, H3O+
O2, H3O+
H
H
OH
OH
H
H
*
*
OH
H
H
R
Zr
R
Zr
Cl
Cl
H
Cl
Cl
H
8a-g
7a-g
2
H
1
Scheme 1.

L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
21
Table 1
Reaction of alkenes 3aeg with AlEt3, catalyzed by complexes 1 or 2 (mole ratio [Zr]: alkene: AlEt3 ¼ 4:50:60, reaction time 24 h, 20 ꢀC).
Entry
Alkene
Solvent
Alkene
Product ratio,c % (ee%, R/S)
[a]
25 (7) (CH2Cl2)
D
conversion, %
4
5
6
Catalyst 1
1
2
3
4
1-Hexene (3a)
S6H12
S6H14
ea
79
65
99
99
76 (34, S)
86 (36, S)
81 (6, S)
10
14 (8, S)
9
30
11
e
þ3.3 (c ¼ 0.4) [4]
þ1.5 (c ¼ 2.3)
10
25
e
45 (<1, S)
5
6
7
1-Heptene (3b)
S6H12
S6H14
42
13
90
66 (37, S)
47 (24, S)
68 (17, S)
24
53
20
8
e
b
C6H6
2
8
9
10
11
12
1-Octene (3c)
1-Nonene (3d)
S6H12
11
61
98
23
70
24 (35, S)
35 (12, S)
51 (10, S)
50 (23, S)
44 (13, S)
26
10
35
18
20
50
16
11
33
6
þ2.5 (c ¼ 1.0)
þ1.1 (c ¼ 0.5)
b
S6H14
b
C6H6
S6H12
b
C6H6
13
14
15
16
17
1-Decene (3e)
S6H12
S6H14
18
42
94
55
50 (24, S)
55 (26, S)
57 (2, S)
29 (14, S)
34 (20, S)
38
37
23
51
46
11
8
14
20
20
þ2.4 (c ¼ 1.3)
þ1.3 (c ¼ 2.7)
b
C6H6
ea
e
56 (15 h)
18
19
20
4-Methyl-1-pentene (3f)
S6H12
C6H6
53
95
91
55 (25, S)
75 (15, S)
55 (10, S)
45
10
37
e
10
8
þ1.4 (c ¼ 1.4)
b
e
21
22
Vinylcyclohexane
(3g)
C6H6
e
30
74
77 (24, R)
70 (6, R)
13
7
10
23
þ4.8 (c ¼ 0.9)d
þ1.2 (c ¼ 3.3)
Catalyst 2
23
3a
3e
S6H14
78
67 (26, R)
24
9
ꢁ3.5 (s ¼ 1.3) [4],e
ꢁ0.6 (c ¼ 1.6)
24
25
26
S6H14
S6H12
e
65
58
77
66 (10, R)
66 (7, R)
59 (9, R)
18
17
19
16
17
22
27
28
3f
3g
S6H6
e
40
66
60 (12, R)
79 (6, S)
40
16
-
5
ꢁ1.0 (c ¼ 2.3)
ꢁ1.0 (c ¼ 2.1)
a
2 mol% [Zr].
Solvent volume is reduced to 10 times.
Determined by GC-MS of deuterolysis products.
Lit. data for (2S)-cyclohexylbutane-l,4-diol: [
b
c
d
e
25
a
]
D
¼ ꢁ17.5 (c ¼ 0.49, EtOH) [5a].
25
Lit. data for (2R)-butyl-1,4-butanediol: [
a
]
¼ ꢁ1 (c ¼ 1.5, EtOH) [5b].
D
intermediate of the cycloalumination reaction is five-membered
complex 12 [12], which is formed from the alkylchloride 11,
responsible for the carboalumination pathway (Scheme 2). It is
also known that stereoselectivity of zirconocene complexes in
alkene polymerization may depend on the conformational
alkenes, substituted with bulky i-butyl-, and cyclohexyl-groups,
have to “find” the least sterically hindered conformers, thereby
decreasing the rate and the enantioselectivity of the reaction. As
a result, the “KeyeLock” principle is realized here, while a high
reaction enantioselectivity is achieved due to the perfect fit
between the geometry of Zr,Al-complex as the catalytically active
center and the substrate.
behavior of the substituted
h
5- ligands [13,14]. Apparently, the
reaction of Zr complexes with AlEt3 gives the definite rotamers of
Zr,Al-complex 12 (Scheme 2), which populations and effective
concentration change with the reaction conditions (solvent,
temperature, reagent ratio).
3. Conclusions
The analysis of complex 12 possible conformers shows that
a large number of rotamers could exist (incidentally, the number of
rotamers can be much greater than indicated in Scheme 2).
Nevertheless, only a few conformers, for example, 12aec,e, has Zre
It was shown that the enantioselectivity of the catalytic alkene
cycloalumination depends on the catalyst and the alkene structure,
as well as on the solvent nature. The reaction of the terminal
alkenes with AlEt3, catalyzed with complex 1, in hydrocarbon
solvents gives predominantly S-enantiomers of 3-alkylsubstituted
aluminacyclopentanes with 24e37%ee. Complex 2 shows smaller
stereoinduction effect and provides R-enantiomers of alumi-
nacyclopentanes with 6e26%ee.
C
bond accessible for alkene coordination. Thus, the cyclo-
alumination reaction runs under a kinetic control, where the steric
factor prevails, and the maximum reaction rate is achieved for the
less constrained conformers.
Moreover, the kinetic control is confirmed by the fact that the
increasing size of the alkene substituent decreases the substrate
conversion and enantiomeric excess of the cyclic OAC. Probably,
Also, it was shown that MTPA and (R)-2-phenylselenopropanoic
acid appears to be effective for enantiomeric excess estimation of
alkyl-1,4-butanediols obtained from aluminacyclopentanes.
b-

22
L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
Et
AlEt
R'
Cp Zr
2
3
EtAl
Cp Zr
Cp ZrCl
2
2
2
-C H
2
Cl
12
AlEt
2
Cl AlEt
11
6
3
R'
R*
R*
R*
R*
R*
R*
R*
Cl
R*
Cl
Cl
R*
R*
Cl
Cl
Al
Al
Al
Al
Al
Zr
AlEt
2
e
Cl
a
b
c
d
R*
R*
12
R*
Cl
Cl
R*
Al
R*
Cl
R*
R*
Cl
Cl
R*
Al
R*
Al
R*
Al
Al
e'
d'
c'
a'
b'
Scheme 2.
4. Experimental section
accumulation (w30,000 sc). Optical rotation angles [
a]
D
were
determined on a Perkin Elmer-341 polarimeter.
4.1. General
5. Synthesis of (D)-3-[(10S,20S,50R)-20-Isopropyl-50-
All operations with organometallic compounds were carried out
under argon using Schlenk techniques. Solvents (benzene, hexane,
cyclohexane) were dried by refluxing over i-Bu2AlH and freshly
distilled prior to use. Methylene chloride was dried over P2O5. THF
was freshly distilled from sodium/benzophenone. Commercially
available 98% AlEt3 were involved in the reactions. Catalysts 1, 2
were prepared from (þ)-3-[(10S,20S,50R)-20-isopropyl-50-methyl-
cyclohexyl]indene (3-neomenthylindene) and ZrCl4 [(99.5%,
Aldrich) or CpZrCl3 using the standard techniques [6,13]. Complex 2
is unstable in air and light, especially in solution, therefore, it was
synthesized immediately prior to use. (R)-Phenylselenopropanoic
acid was synthesized according to the procedure described in
Ref. [7].
methylcyclohexyl]indene (3-neomenthylindene) (improved)
Indene (80 mmol, 9.4 ml) was added dropwise to a suspension of
80 mmol of NaH (3.2 g of 60% NaH in paraffin) in 150 ml of THF. The
mixture was stirred at room temperature to complete NaH disso-
lution. To this mixture a solution of 19.4 g (62.5 mmol) of
(ꢁ)-menthyl tosylate in 100 ml of THF was added dropwise at 0 ꢀC.
The mixture was stirred for 1 h at room temperature and then
refluxed for 72 h. The mixture was hydrolyzed with water (100 ml).
The organic phase was separated and the aqueous phase was
extracted twice with ether (50-ml portions). The combined
organic layers were dried over Na2SO4. The solvent was evaporated
in vacuum and the remaining residue was separated by column
chromatography on silica gel (hexane/CHCl3 7:1). 3-Neomenthy-
lindene (7 g, 44 %) was obtained by vacuum distillation (110 ꢀC,
10 mm Hg) of the first fractions of column chromatography. Physical
chemistry constants and NMR characteristics of obtained 3-
neomenthylindene were identical to the literature data [13].
The 1H and 13C NMR spectra were recorded on a Bruker
AVANCE-400 spectrometer (400.13 MHz (1H), 100.62 MHz (13C),
76.35 MHz (77Se)). Benzene-d6, toluene-d8 and CDCl3 were used as
solvents. The samples were prepared in standard tubes of 5 mm
diameter. Chemical shifts are internally referenced to the TMS
signal. NMR 77Se shifts are given relative to the Me2Se. Two-
dimensional NMR spectra (COSY, HSQC, HMBC) were measured
with standard pulse sequences.
5.1. Reaction of terminal alkenes with AlEt3 in the presence of
complexes 1 or 2
The hydrolysis products of the reaction mixture were analyzed
on a Carlo Erba gas chromatograph (He, column 50,000 ꢂ 0.32 mm,
fixed phase ‘Ultra-1’, flame-ionization detector). Mass spectra were
obtained on MD 800, TRIO 1000 VG Masslab (Great Britain)
spectrometer.
The enantioselectivity of the carbo- and cyclometallation reac-
tions was determined from the enantiomeric purity of corre-
sponding alcohols, which were derived after the oxidation and
hydrolysis of a reaction media. The alcohols were derivatised with
A 10 ml flask equipped with a magnetic stirrer and filled with
argon was loaded with 0.02e0.075 mmol of complexes 1 or 2, 3 ml
of a solvent (benzene, hexane, cyclohexane), 1 mmol of alkenes
(3aeg) and 1.2 mmol of AlEt3. The reaction mixture was stirred for
24 h at 22 ꢀC. Then, a part of the reaction mixture was decomposed
with 10% HCl or DCl at 0 ꢀC. The products were extracted with
benzene; further, the organic layer was dried over Na2SO4 and
analyzed by GC or GC-MS. Another part of the reaction mixture was
cooled to 0 ꢀC and a dry oxygen was passed through for 2 h. The
resultant mixture was further stirred under oxygen atmosphere for
24 h, and then treated with 10% HCl and extracted with Et2O. The
organic layer was dried over Na2SO4, filtered, and concentrated.
Alcohols 7aeg were separated by column chromatography. The
chromatography of the mixture 7 þ 8 on silica gel (hexane/Et2O
(S)-(þ)-
a-methoxy-a-trifluoromethylphenylacetyl chloride [(S)-
MTPA-Cl] or (R)-phenylselenopropanoic acid [(R)-PSPA], and the
obtained diastereomeric esters analyzed by 1H and 13C NMR
spectroscopy. Analysis of the (R,R)- and (R,S)-diastereomers of the
MTPA esters of the
b-substituted 1,4-butanediols 7aeg was carried
out using 13C NMR spectra obtained as a result of long-term

L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
23
4:1) provided compound 8; then the column was washed with
acetone to give 7aeg as a colorless oils. The organic fractions were
concentrated and dried over Na2SO4. MTPA esters of 7aeg were
prepared as described in Ref. [6] PSPA esters of 7aeg were prepared
according to Ref. [7].
(CDCl3) dC 26.6, 26.7, 26.8 (C7, C8, C9), 30.1, 30.2 (C6, C10), 33.4 (C3),
40.2 (C5), 45.0 (C2), 61.9 (C4), 64.9 (C1).
5.1.7. (R)-MTPA ester of (2R,S)-pentyl-1,4-butanediol (9b)
1H NMR (C7D8) dH 0.85 (3H, t, 3JHH ¼ 7.1 Hz, CH3), 0.95e1.25 (6H,
m, CH2(CH2)3CH3), 1.25e1.49 (2H, m, CH2CH2OH), 1.42e1.56 (1H, m,
CH), 1.51e1.72 (2H, m, CH2CHCH2OH), 3.88 (1H, dd, 2JHH ¼ 11.1 Hz,
3JHH ¼ 5.1 Hz, CHCHHOH), 3.94e4.08 (1H, m, CHCHHOH), 3.94e4.13
(2H, m, CH2CH2OH), 3.40 (6H, s, OCH3), 6.85e7.35 (4H, m, Ph), 7.52e
7.92 (6H, m, Ph). 13C NMR (C7D8) dC 13.7 (C9), 22.3 (C8), 25.9 (C6),
29.66 (RRR), 29.84 (SRR) (C3), 30.36 (SRR), 30.44 (RRR) (C5), 31.7 (C7),
33.92 (RRR), 34.02 (SRR) (C2), 54.8 (OCH3), 63.5 (C4), 67.5 (C1), 123.7
(q, JCeF ¼ 287 Hz, CF3), 125.2, 127.3, 127.6, 127.8, 132.4, 133.8 (Ph),
166.0, 168.9 (C]O).
5.1.1. (2R,S)-pentyl-1,4-butanediol (7b)
3
1H NMR (CDCl3) dH 0.89 (3H, t, JHH ¼ 6.4 Hz, SO3), 1.17e1.40
(8H, m, SO2), 1.52e1.76 (3H, m, CHCH2CH2OH), 3.47 (1H, dd,
3
2JHH ¼ 10.8 Hz, JHH ¼ 6.8 Hz, CHCHHOH), 3.59e3.70 (1H, m,
CHSHOPO) 3.64e3.72 (1H, m, CH2SHOPO), 3.74e3.84 (1H, m,
CH2SHOPO). 13C NMR (CDCl3) dC 14.1 (C9), 22.6 (C8), 26.8 (C6), 32.1
(C7), 31.7 (C5), 35.8 (C3), 39.4 (C2), 61.2 (C4), 66.4 (C1).
5.1.2. (2R,S)-hexyl-1,4-butanediol (7c)
n2D2 ¼ 1.4555, IR (KBr, cmꢁ1): 3341, 2926, 1465, 1045. 1H NMR
5.1.8. (R)-MTPA ester of (2R,S)-hexyl-1,4-butanediol (9c)
3
3
(400.13 MHz, CDCl3) dH 0.89 (3H, t, JHH ¼ 6.9 Hz, SO3), 1.17e1.38
1H NMR (C7D8) dH 0.97 (3H, t, JHH ¼ 7.3 Hz, CH3), 1.06e1.24
(10H, m, SO2), 1.53e1.77 (2H, m, CHCH2CH2OH), 1.59e1.72 (2H,
(10H, m, CH(CH2)5CH3), 1.41e1.51 (2H, m, CH2CH2OH), 1.50e1.58
2
3
2
3
m, CHCH2OH), 3.50 (1H, dd, JHH ¼ 10.4 Hz, JHH ¼ 7.2 Hz,
CHCHHOH), 3.63e3.72 (1H, m, CHSHOPO) 3.62e3.72 (m, 1H,
CH2SHOPO), 3.75e3.84 (m, 1H, CH2SHOPO). 13C NMR (CDCl3) dC
14.1 (C10), 22.6 (C9), 27.1 (C6), 29.6 (C7), 31.8 (C5), 31.8 (C8), 35.8 (C3),
39.4 (C2), 61.2 (C4), 66.4 (C1).
(1H, m, CHCH2OH), 3.94 (1H, dd, JHH ¼ 11.1 Hz, JHH ¼ 5.1 Hz,
CHCHHOH), 4.01e4.17 (3H, m, CHCHHOH, CH2CH2OH), 3.47 (6H, s,
OCH3), 6.91e7.10 (4H, m, Ph), 7.62e8.05 (6H, m, Ph). 13C NMR (C7D8)
dC 14.0 (C10), 22.7 (C9), 26.5 (C6), 29.3 (C7), 29.77 (RRR), 29.94 (SRR)
(C3), 30.52 (SRR), 31.50 (RRR) (C5), 31.6 (C8), 34.03 (RRR), 34.13 (SRR)
(C2), 54.9 (OCH3), 63.5 (C4), 67.5 (C1), 84.7 (q, J ¼ 27.6 Hz, CH3OC),
124.3 (q, JCeF ¼ 286 Hz, CF3), 127.2e130.2 (Ph), 166.0 (C]O).
5.1.3. (2R,S)-heptyl-1,4-butanediol (7d)
3
1H NMR (CDCl3) dH 0.90 (3H, t, JHH ¼ 7.04 Hz, SO3), 1.20e1.40
(m, 12H, SO2), 1.52e1.78 (3H, m, CHCH2CH2OH), 3.52 (1H, dd,
5.1.9. (R)-MTPA ester of (2R,S)-heptyl-1,4-butanediol (9d)
3
2JHH ¼ 10.7 Hz, JHH ¼ 6.8 Hz, CHCHHOH), 3.62e3.73 (1H, m,
1H NMR (C7D8) dH 0.91 (3H, t, 3JHH ¼ 7.1 Hz, CH3),1.02e1.26 (12H,
m, CH(CH2)6CH3), 1.36e1.52 (2H, m, CH2CH2OH), 1.55e1.64 (1H, m,
CHCH2OH), 3.90 (1H, dd, 2JHH ¼ 11.1 Hz, 3JHH ¼ 5.3 Hz, CHCHHOH),
3.96e4.18 (3H, m, CHCHHOH, CH2CH2OH), 3.45 (6H, s, OCH3), 6.77e
7.35 (4H, m, Ph), 7.50e7.93 (6H, m, Ph). 13C NMR (C7D8) dC 14.0 (C11),
22.7 (C10), 26.4 (C6), 29.2 (C8), 29.7 (C7), 29.83 (RRR), 29.98 (SRR)
(C3), 30.48 (SRR), 30.58 (RRR) (C5), 31.6 (C9), 34.09 (RRR), 34.20 (SRR)
(C2), 54.9 (OCH3), 63.6 (C4), 67.6 (C1), 84.7 (q, J ¼ 27.8 Hz, CH3OC),
123.7 (q, JCeF ¼ 288 Hz, CF3), 127.2e130.2 (Ph), 166.1, 166.2 (C]O).
CHSHOPO) 3.62e3.73 (1H, m, CH2SHOPO), 3.77e3.85 (1H, m,
CH2SHOPO). 13C NMR (CDCl3) dC 14.1 (C11), 22.7 (C10), 27.1 (C6) 29.3
(C8), 29.9 (C7), 31.7 (C5), 31.9 (C9), 35.8 (C3), 39.3 (C2), 61.3 (C4), 66.4
(C1).
5.1.4. (2R,S)-octyl-1,4-butanediol (7e)
n2D2 ¼ 1.4565, IR (KBr, cmꢁ1): 3329, 2925, 1465, 1046. 1H NMR
(CDCl3) dH 0.86 (3H, t, 3JHH ¼ 6.4 Hz, SO3), 1.13e1.37 (14H, m, SO2),
2
1.50e1.69 (3H, m, CHCH2CH2OH), 3.40 (1H, dd, JHH ¼ 10.8 Hz,
3JHH ¼ 6.8 Hz, CHCHHOH), 3.56e3.63 (1H, m, CHSHOPO) 3.56e
3.59 (1H, m, CH2SHOPO), 3.69e3.75 (1H, m, CH2SHOPO). 13C
NMR (CDCl3) dC 14.1 (C12), 22.7 (C11), 27.1 (C6) 29.3 (C9), 29.6 (C8),
29.9 (C7), 31.7 (C5), 31.9 (C10), 35.9 (C3), 39.4 (C2), 61.2 (C4), 66.5 (C1).
5.1.10. (R)-MTPA ester of (2R,S)-octyl-1,4-butanediol (9e)
3
1H NMR (C7D8) dH 0.90 (3H, t, JHH ¼ 6.8 Hz, CH3), 0.97e1.12
(12H, m, CH(CH2)6CH2CH3), 1.12e1.21 (2H, m, CH2CH3), 1.41e1.50
(2H, m, CH2CH23OH), 1.50e1.59 (1H, m, CH), 3.85 (1H, dd,
2JHH ¼ 11.2 Hz, JHH ¼ 6.4 Hz, CHCHHOH), 3.94e4.18 (3H, m,
CHCHHOH, CH2CH2OH), 3.48 (6H, s, OCH3), 7.05e7.14 (4H, m, Ph),
7.51e7.89 (6H, m, Ph). 13C NMR (C7D8) dC 14.0 (C12), 22.6 (C11), 26.5
(C6), 29.3 (C9), 29.5 (C8), 29.7 (C7) 29.73 (RRR), 29.79 (SRR) (C3),
30.57 (SRR), 30.65 (RRR) (C5), 31.9 (C10) 34.06 (RRR), 34.17 (SRR) (C2),
54.96 (OCH3), 63.7 (C4), 67.7 (C1), 84.8 (q, J ¼ 27.0 Hz, CH3OC), 123.0
(q, JCeF ¼ 288 Hz, CF3), 127.3e130.2 (Ph), 166.1 (C]O).
5.1.5. (2R,S)-isobutyl-1,4-butanediol (7f)
n2D2 ¼ 1.4520, IR (KBr, cmꢁ1): 3329, 2955, 1468, 1040. 1H NMR
(CDCl3) dH 0.88 (6H, d, JHH ¼ 6.0 Hz, SO3), 0.90 (6H, d, JHH ¼ 6.4 Hz,
SO3), 1.04e1.22 (2H, m, SO2), 1.57e1.68 (1H, m, SH), 1.49e1.62
(1H, m, CHHSH2PO), 1.64e1.74 (1H, m, CHHSH2PO), 1.67e1.78
2
3
(1H, m, CHCH2OH), 3.43 (1H, dd, JHH ¼ 10.8 Hz, JHH ¼ 7. Hz,
2
3
CHSHOPO), 3.64 (1H, dd, JHH ¼ 10.8 Hz, JHH ¼ 4.0 Hz,
CHSHOPO) 3.60e3.68 (1H, m, CH2SHOPO), 3.76 (1H, ddd,
2JHH ¼ 10.4 Hz, 3JHH ¼ 6.4 Hz, 3JHH ¼ 4.4 Hz, CH2SHOPO). 13C NMR
(CDCl3) dC 22.7, 22.9 (C7, C8), 25.2 (C6), 36.0 (C3), 37.1 (C2), 41.1 (C5),
61.1 (C4), 66.5 (C1).
5.1.11. (R)-MTPA ester of (2R,S)-isobutyl-1,4-butanediol (9f)
1H NMR (C7D8) dH 0.67 (3H, d, 3J ¼ 6.0 Hz, CH3), 0.68 (3H, d,
3J ¼ 6.0 Hz, CH3), 0.76e0.82 (1H, m, (CH3)2CHCHH), 0.89e1.0 (1H,
m, (CH3)2CHCHH), 1.25e1.49 (2H, m, CH2CH2OH), 1.27e1.36 (1H, m,
(CH3)2CH), 1.54e1.68 (1H, m, CHCH2OH), 3.83e3.91 (1H, m,
CHCHHOH), 3.95e4.03 (1H, m, CHCHHOH), 3.95e4.10 (2H, m,
5.1.6. (2R,S)-cyclohexyl-1,4-butanediol (7g)
n2D2 ¼ 1.4910, IR (KBr, cmꢁ1): 3329, 2923, 1449, 1043. 1H NMR
(CDCl3) dH 0.95e1.12 (2Hax, m, Cy), 1.57e1.72 (2Heq, m, Cy), 1.13e
1.31 (2Hax, m, Cy), 1.71e1.80 (2Heq, m, Cy), 1.015e1.2 (1Hax, m,
Cy), 1.61e1.71 (1Heq, m, Cy), 1.34e1.44 (1H, m, CHCHCH2OH), 1.45e
1.53 (1H, m, CHCHCH2OH), 1.54e1.66 (1H, m, CHCHHCH2OH), 1.68e
CH2CH2OH), 3.40 (6H, s, OCH3), 6.74e7.33, 7.48e7.90 (10H, Ph). 13
C
NMR (C7D8) dC 21.8 (C8), 24.77 (SRR), 24.82 (RRR) (C6), 22.5 (C7),
30.21 (RRR), 30.38 (SRR) (C3), 31.64 (RRR), 31.78 (SRR) (C2), 39.82
(SRR), 40.00 (RRR) (C5), 63.48 (RRR), 63.56 (SRR) (C4), 67.7 (C1), 54.93
(OCH3), 84.7 (q, J ¼ 26.2 Hz), 123.1 (q, JCeF ¼ 287 Hz), 127.3e130.2
(Ph), 166.1, 166.2 (C]O).
2
1.78 (1H, m, CHCHHCH2OH), 3.58 (1H, dd, JHH ¼ 10.6 Hz,
2
3JHH ¼ 7.8 Hz, CHSHOPO), 3.71 (1H, dd, JHH ¼ 10.8 Hz,
2
3JHH ¼ 3.6 Hz, CHSHOPO), 3.64 (1H, ddd, JHH ¼ 10.8 Hz,
5.1.12. (R)-MTPA ester of (2R,S)-cyclohexyl-1,4-butanediol (9g)
1H NMR (C7D8) dH 0.58e0.75 (2H, m, CHaxHCH (Cy)), 1.22e1.39
(2H, m, CHHeqCH (Cy)), 0.89e1.11 (3H, m, CHaxHCH2 (Cy)), 1.48e
3
3JHH ¼ 8.0 Hz , JHH ¼ 4.4 Hz, CH2SHOPO), 3.81 (1H, ddd,
2JHH ¼ 10.8 Hz, 3JHH ¼ 6.4 Hz , 3JHH ¼ 4.4 Hz, CH2SHOPO). 13C NMR

24
L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
1.62 (3H, m, CHHeqCH2 (Cy)), 1.00e1.13 (1H, m, CHCHCH2OH), 1.29e
1.39 (1H, m, CHCH2OH), 1.26e1.36 (1H, m, CHHCH2OH), 1.44e1.54
(1H, m, CHHCH2OH), 3.91 (1H, dd, 2J ¼ 11.6 Hz, 3J ¼ 5.7 Hz,
CH2CHHOH) (SRR), 3.95e4.04 (1H, m, CH2CHHOH) (RRR), 4.07e4.15
(1H, m, CH2CHHOH) (SRR, RRR), 3.93e4.15 (2H, m, CHCH2OH), 3.41
(6H, s, OCH3), 6.75e7.58 (10H, Ph). 13C NMR (C7D8) dC 26.16, 26.30,
26.32 (C8, C9, C10, (Cy)), 29.3, 29.4 (C6, C7, (Cy)), 27.12 (SRR), 27.23
(RRR) (C3), 38.39 (RRR), 38.47 (SRR) (C5), 39.15 (C2), 64.11 (C4), 66.24
(SRR), 66.28 (RRR) (C1), 54.9 (OCH3), 84.5 (q, J ¼ 26.4 Hz, COCH3),
123.5 (q, JCeF ¼ 288 Hz), 127.3e130.2 (Ph), 166.0 (C]O).
m, Ph), 7.55e7.65 (4H, m, Ph). 13C NMR (CDCl3) dC 14.1 (C11), 17.67,
17.70, 17.74 (CH3CH), 22.7 (C10), 26.7 (C6), 29.2 (C8), 29.9 (C7), 30.11
(SRR), 30.17 (RRR) (C3), 31.0 (C5), 31.9 (C9), 34.42 (RRR), 34.46 (SRR)
(C2), 37.3 (SeCH), 63.1 (C4), 67.17 (RRR), 67.20 (SRR) (C1), 127.7, 128.0,
128.9, 129.04, 129.2, 135.4, 135.6 (Ph), 173.5, 173.6 (C]O). 77Se NMR
(CDCl3) dSe 453.40 (RRR), 453.82 (RRR), 454.02 (SRR), 454.21 (SRR).
5.1.17. (R)-phenylselenopropanoic acid ester of (2R,S)-octyl-1,4-
butanediol (10e)
1H NMR (CDCl3) dH 0.87 (3H, t, CH3CH2, 3J ¼ 6.5 Hz), 1.20e1.30
(6H, m, (CH2)3), 1.50 (2H, pent, CHCH2CH2O, 3J ¼ 6.8 Hz), 1.45e
1.56 (1H, m, CH2CHCH2O), 1.54 (3H, d, CH3CH, 3J ¼ 7.1 Hz), 1.55
(3H, d, CH3CH, 3J ¼ 7.0 Hz), 3.70e3.84 (2H, m, CH3CH), 3.87e4.01
(2H, m, CHCH2HO), 3.98e4.08 (2H, m, CH2CH2O), 7.22e7.39 (6H,
m, Ph), 7.52e7.64 (4H, m, Ph). 13C NMR (CDCl3) dC 14.1 (C12), 17.66,
17.70, 17.75 (CH3CH), 26.6 (C9), 29.3 (C8), 29.5 (C7), 29.9 (C6), 31.0
(C5), 30.09 (SRR), 30.15 (RRR) (C3), 31.9 (C10), 34.40 (RRR), 34.44
(SRR) (C2), 37.3 (SeCH), 63.0 (C4), 67.13 (RRR), 67.15 (SRR) (C1), 127.1,
127.7, 128.42, 128.46, 129.0, 129.04, 135.4, 135.6 (Ph), 173.4, 173.5
(C]O). 77Se NMR (CDCl3) dSe 453.44 (RRR), 453.87 (RRR), 454.06
(SRR), 454.27 (SRR).
5.1.13. (R)-phenylselenopropanoic acid ester of (2R,S)-butyl-1,4-
butanediol (10a)
1H NMR (CDCl3) dH 0.89 (3H, t, CH3CH2, 3J ¼ 6.8 Hz), 1.20e1.29
(4H, m, (CH2)2), 1.22e1.31 (2H, m, CH3CH2), 1.54 (3H, d, CH3CH,
3J ¼ 7.2 Hz), 1.55 (3H, d, CH3CH, 3J ¼ 7.2 Hz), 1.51 (2H, pent,
CHCH2CH2O, 3J ¼ 6.8 Hz), 1.58e1.67 (1H, m, CH2CHCH2O), 3.73e
3.83 (2H, m, CH3CH), 3.91 (1H, dd, CHCHHO, 2J ¼ 11.2 Hz,
3J ¼ 5.6 Hz), 3.97 (1H, dd, CHCHHO, 2J ¼ 11.2 Hz, 3J ¼ 5.6 Hz), 3.98e
4.09 (2H, m, CH2CH2O), 7.25e7.35 (6H, m, Ph), 7.55e7.62 (4H, m,
Ph). 13C NMR (CDCl3) dC 14.0 (C8), 17.65, 17.70, 17.73 (CH3CH), 22.8
(C7), 28.8 (C6), 30.7 (C5), 30.10 (RRR), 30.17 (SRR) (C3), 34.39 (RRR),
34.42 (SRR) (C2), 37.6 (SeCH), 63.0 (C4), 67.13 (RRR), 67.16 (SRR) (C1),
173.4, 173.5 (C]O), 127.90, 127.94, 127.99, 128.42, 128.45, 129.00,
129.02, 135.4, 135.6, 135.97 (Ph). 77Se NMR (CDCl3) dSe 453.50 (RRR),
453.89 (RRR), 454.08 (SRR), 454.25 (SRR).
5.1.18. (R)-phenylselenopropanoic acid ester of (2R,S)-isobutyl-1,4-
butanediol (10f)
1H NMR (CDCl3) dH 0.83e0.92 (6H, m, CH3), 0.99e1.22 (2H, m,
CHCH2CH), 1.44e1.52 (2H, m, CHCH2CH2O), 1.45e1.52 (1H, m,
CH2CHCH2O), 1.53e1.60 (6H, m, CH3CH), 1.54e1.66 (1H, m,
CH3CHCH3), 3.74e3.86 (2H, m, CH3CH), 3.86e4.03 (2H, m,
CHCH2O), 3.99e4.08 (2H, m, CH2CH2O), 7.23e7.37 (6H, m, Ph),
7.56e7.64 (4H, m, Ph). 13C NMR (CDCl3) dC 17.7 (CH3CH), 23.7 (C7),
23.8 (C8), 25.16 (C6), 30.47 (RRR), 30.56 (SRR) (C3), 32.21 (RRR), 32.27
(SRR) (C2), 37.34, 37.38 (SeCH), 40,51 (RRR), 40.54 (SRR) (C5), 62.96
(RRR), 63.0 (SRR) (C4), 67.4 (C1), 127.22, 127.72, 128.44, 128.47,
129.01, 129.04, 135.40, 135.57, 135.60 (Ph), 173.4, 173.5 (C]O). 77Se
NMR (CDCl3) dSe 453.32 (RRR), 454.13 (RRR), 454.37 (SRR), 454.42
(SRR).
5.1.14. (R)-phenylselenopropanoic acid ester of (2R,S)-pentyl-1,4-
butanediol (10b)
1H NMR (CDCl3) dH 0.90 (3H, t, CH3CH2, 3J ¼ 6.9 Hz), 1.19e1.39
(8H, m, (CH2)4), 1.557 (3H, d, CH3CH, 3J ¼ 7.0 Hz), 1.564 (3H, d,
CH3CH, 3J ¼ 7.1 Hz), 1.51 (2H, pent, CHCH2CH2O, 3J ¼ 6.8 Hz), 1.59e
1.69 (1H, m, CH2CHCH2O), 3.74e3.85 (2H, m, CH3CH), 3.93 (1H, dd,
CHCHHO, 2J ¼ 11.1 Hz, 3J ¼ 5.6 Hz), 3.98 (1H, dd, CHCHHO,
2J ¼ 11.1 Hz, 3J ¼ 5.3 Hz), 4.00e4.15 (2H, m, CH2CH2O), 7.24e7.39
(6H, m, Ph), 7.56e7.65 (4H, m, Ph). 13C NMR (CDCl3) dC 14.1 (C9),
17.67, 17.71, 17.75 (CH3CH), 22.6 (C8), 26.3 (C6), 32.0 (C7), 30.12 (SRR),
30.14 (RRR) (C3), 30.9 (C5), 34.42 (RRR), 34.46 (SRR) (C2), 37.3 (SeCH),
63.0 (C4), 67.15 (RRR), 67.18 (SRR) (C1), 173.4, 173.5 (C]O), 127.7,
128.43, 128.46, 129.01, 129.04, 135.4, 135.5 (Ph). 77Se NMR (CDCl3)
dSe 453.36 (RRR), 453.78 (RRR), 453.98 (SRR), 454.16 (SRR).
5.1.19. (R)-phenylselenopropanoic acid ester of (2R,S)-cyclohexyl-
1,4-butanediol (10g)
1H NMR (C7D8) dH 0.92e1.04 (2H, m, CHaxHCH (Cy)), 1.54e1.63
(2H, m, CHHeqCH (Cy)), 1.11e1.23 (3H, m, CHaxHCH2 (Cy)), 1.57e
1.67 (3H, m, CHHeqCH2 (Cy)), 1.28e1.39 (1H, m, CHCHCH2O, Cy),
1.56 (6H, d, CH3CH, 3J ¼ 7.4 Hz), 1.54e1.63 (2H, m, CH2CH2O), 1.58e
1.67 (1H, m, CHCH2O), 3.72e3.84 (2H, m, CHCH3), 3.97e4.11 (2H, m,
CH2CH2O), 3.90e3.98 (1H, m, CHCHHO), 4.02e4.10 (1H, m,
CHCHHO), 7.22e7.41 (6H, m, Ph), 7.55e7.69 (4H, m, Ph). 13C NMR
(CDCl3) dC 17.70 (CH3CH), 26.6, 26.7, 29.99, 30.01 (Cy), 29.74 (SRR),
29.77 (RRR) (C3), 37.4 (SeCH), 38.96 (RRR), 39.04 (SRR) (C5, Cy), 39.6
(C2), 63.8 (C4), 65.8 (C1), 127.6, 127.7, 128.4, 128.9, 129.00, 129.03,
134.8, 135.4, 135.6, 135.9, (Ph), 173.1 (C]O). 77Se NMR (CDCl3) dSe
453.39 (SRR), 453.88 (SRR), 453.64 (RRR), 454.22 (RRR).
5.1.15. (R)-phenylselenopropanoic acid ester of (2R,S)-Hexyl-1,4-
butanediol (10c)
1H NMR (CDCl3) dH 0.90 (3H, t, CH3CH2, 3J ¼ 6.3 Hz), 1.21e1.38
(10H, m, (CH2)5), 1.50 (2H, pent, CHCH2CH2O, 3J ¼ 6.2 Hz), 1.58
(6H, d, CH3CH, 3J ¼ 6.9 Hz), 1.61e1.69 (1H, m, CH2CHCH2O), 3.73e
3.87 (2H, m, CH3CH), 3.92 (1H, dd, 3J ¼ 5.3 Hz, 2J ¼ 10.9 Hz,
CHCHHO), 3.98 (1H, dd, 3J ¼ 6.0 Hz, 2J ¼ 10.9 Hz, CHCHHO), 3.99e
4.11 (2H, m, CH2CH2O), 7.17e7.39 (6H, m, Ph), 7.53e7.69 (4H, m, Ph).
13C NMR (CDCl3) dC 14.1 (C10), 17.67, 17.71, 17.75 (CH3CH), 22.6 (C9),
26.6 (C6), 29.9 (C7), 30.11 (SRR), 30.16 (RRR) (C3), 30.9 (C5), 31.8 (C8),
34.41 (RRR), 34.45 (SRR) (C2), 37.3 (SeCH), 63.1 (C4), 67.18 (RRR),
67.21 (SRR) (C1), 127.7, 128.45, 128.49, 128.99, 135.4, 135.6 (Ph),
173.5, 173.6 (C]O). 77Se NMR (CDCl3) dSe 453.58 (RRR), 454.04
(RRR), 454.23 (SRR), 454.43 (SRR).
Acknowledgements
The authors thank the Russian Foundation of Basic Research
(gs1) (grant no. 11-03-00210-a) and the Russian Ministry of
Education and Science for financial support. The authors are
grateful to Prof. Ananikov V.P. and Dr. Orlov N.V. for valuable
discussions and a gift of a sample of (R)-phenylselenopropanoic
acid.
5.1.16. (R)-phenylselenopropanoic acid ester of (2R,S)-heptyl-1,4-
butanediol (10d)
1H NMR (CDCl3) dH 0.90 (3H, t, CH3CH2, 3J ¼ 6.8 Hz), 1.20e1.34
(12H, m, (CH2)6), 1.51 (2H, pent, CHCH2CH2O, 3J ¼ 6.8 Hz), 1.55
(3H, d, CH3CH, 3J ¼ 7.2 Hz), 1.56 (3H, d, CH3CH, 3J ¼ 6.8 Hz), 1.60e
1.67 (1H, m, CH2CHCH2O), 3.73e3.84 (2H, m, CH3CH), 3.92 (1H,
dd, 3J ¼ 5.7 Hz, 2J ¼ 11.1 Hz, CHCHHO), 3.98 (1H, dd, 3J ¼ 5.7 Hz,
2J ¼ 11.1 Hz, CHCHHO), 3.98e4.09 (2H, m, CH2CH2O), 7.24e7.42 (6H,
Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2012.10.021.

L.V. Parfenova et al. / Journal of Organometallic Chemistry 723 (2013) 19e25
25
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