Stereoselectivity of Grignard reaction in the presence of chiral podands and crown ethers

Article abstract of DOI:10.1023/B:RUJO.0000034953.76058.e4

Reactions of ethylmagnesium bromide with benzaldehyde and acetophenone in toluene proceed stereoselectively in the presence of catalytic amounts of chiral podands and crown ethers. Under catalytic conditions theyield of the corresponding alcohols is nearl

Full text of DOI:10.1023/B:RUJO.0000034953.76058.e4

Russian Journal of Organic Chemistry, Vol. 40, No. 2, 2004, pp. 273-277. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 2, 2004,
pp. 301-305.
Original Russian Text Copyright Ó 2004 by Luk’yanenko, Lobach, Leus.
Stereoselectivity of Grignard Reaction in the Presence of Chiral
Podands and Crown Ethers
N. G. Luk’yanenko, A. V. Lobach, and O. N. Leus
Bogatsky Physicochemical Institute, National Academy of Sciences of Ukraine, Odessa, 65080 Ukraine
e-mail: ngl@farlep.net
Received June 19, 2003
Abstract—Reactions of ethylmagnesium bromide with benzaldehyde and acetophenone in toluene proceed
stereoselectively in the presence of catalytic amounts of chiral podands and crown ethers. Under catalytic conditions
theyield of the corresponding alcohols is nearly quantitative. The optical yield varies in the range 9–86% depending
on the catalyst structure.
Enantiodifferentiating qualities of chiral crown ethers
and their acyclic analogs, podands, provide versatile
opportunities for their application as enantioselective
sensors, enantiodifferentiating agents, models of biologic
systems, and catalysts of asymmetrical reactions [1].
Optically active crown ethers relatively seldom were
used as catalysts of phase-transfer catalysis [2].
However examples are known of their successful
application as stereoselective phase-transfer catalysts in
Grignard reaction may be performed also under phase-
transfer conditions in the presence of 5–10 mol% of
crown ether [9].
We report here on the synthesis of new chiral podands
and results of investigating Grignard reaction in the
presence of chiral podands and crown ethers as catalysts
of asymmetricl induction.
As starting chiral synthons for podands synthesis
served tetrol I and diamine II that by alkylation with
tosylate III in dioxane were converted into podand IV
and azapodand V (see the scheme).
aromatic ketones reduction with aminoborane NH BH3
3
[3], Michael [4], and Darzen reactions [5]. Up till now
the possibility of application of chiral podands and crown
ethers as stereoselective catalysts for Grignard reaction
virtually is not investigated. Only reactions of
asymmetrical addition of alkylmagnesium halides to
enones [6] and g-ketoesters [7] were described. In the
first study the catalysis was carried out using complexes
The catalytic and enantiodifferentiating activity of
podands IV and V and chiral compounds that we had
prepared before (chiral podand VI, crown ethers VII
and VIII [10], IX and X [11], and azacrown ethers XI
[12], XII, and XIII [13]) was investigated by an example
of ethylmagnesium bromide reactions with benzaldehyde
and acetophenone in toluene at 0°Ñ in the presence of
2
+
2+
3+
of Zn , Pd and Eu with chiral thiazacrown ethers, in
the second were applied chiral podands originating from
binaphthol.
1
0 mol% of the catalyst. The catalytic activity was
evaluated by the time of complete conversion of the initial
carbonyl compound. Yields of the corresponding alcohols
in all cases attained 90–98% (GLC data). The alcohol
yield in the absence of the catalyst did not exceed 1–2%,
and therefore the non-catalyzed process was disregarded.
We demonstrated formerly that crown ethers in
solution form stable complexes with aryl(alky)magnesium
halides (1:1) that were isolated as individual compounds
[8]. These complexes mildly and highly selectively react
with carbonyl compounds both in ether traditional for the
Grignard reaction and in hydrocarbon solvents. The
The preliminary runs showed that the maximum yield
of the corresponding alcohols was obtained at the ratio
of ethylmagnesium bromide to the carbonyl compound
of 2:1. Under catalysis the yield of the target alcohol
calculated on the reacted carbonyl compound reached a
quantitative value, and any side products are virtually
lacking. The catalytic activity of all crown ethers VII–X
and azacrown ethers XI–XIII studied considerably
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

STEREOSELECTIVITY OF GRIGNARD REACTION
275
Process time, yields, and enantioselectivity of reaction of ethylmagnesium bromide with benzaldehyde and acetophenone in the
presence of chiral ligands IV–XIII in toluene at the ratio of ethylmagnesium bromide to carbonyl compound 2:1
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Ratio of specific rotation of reaction product to the specific rotation of a pure enantiomer expressed as percent. The values [a] for pure
enantiomers of 1-phenyl-1-propanol and 2-phenyl-2-butanol were taken as ± 40.0 [14] and ±18.4 [15] respectively.
D
°
°
exceeded that of acyclic podands IV–VI demonstrating
the decisive contribution of the cyclic structure to
formation of soluble complexes with the reagent (see
table).
metrical induction is of similar order of magnitude. The
highest optical yields in the Grignard reaction were
obtained at the use as catalyst of crown ether XI probably
due to the presence in its molecule of four closely located
asym-metrical centers.
The yield of the corresponding alcohols from aceto-
phenone was regularly by 2–3% higher than from
benzaldehyde; the latter was more disposed to form side
products. The comparison in pairs of catalysts with similar
structures (IV and V, IX and XII, X and XIII) shows
that azapodand V and azacrown ethers XII and XIII are
considerably more efficient catalysts than their oxygen-
containing analogs.The value of the asymmetrical
induction (the optical yield of the product) changes within
these pairs in the same direction as their catalytic activity.
The higher rate and enantiselectivity of the reaction in
the presence of chiral azapodand and azacrown ethers is
likely to be caused by formation of more stable
complexes with reagent molecules than those with the
oxygen-containing analogs.
It should be noted in conclusion that we demonstrated
the possibility to perform asymmetrical Grignard reaction
at the use of chiral podands and crown ethers as catalysts.
The results obtained show sufficiently high enantio-
selectivity of some crown ethers, for instance, VIII, XI–
XIII. Therefore their application to asymmetrical
synthesis involving organomagnesium compounds is
promising.
EXPERIMENTAL
1Í NMR spectra were registered on spectrometer
BrukerAM-250 (250 MHz) in CDCl , internal reference
3
HMDS. Mass spectra were measured on Varian MAT-
112 and MKh-1321 instruments with direct sample
admission into the ion source, ionizing electrons energy
70 eV. Values of [a]D20 were determined on polarimeter
Perkin Elmer 241-MC.
Reactions with acetophenone as compared to those
with benzaldehyde were always slower but afforded the
corresponding alcohol with a higher optical yield. The
reason of this fact is apparently the higher shielding of
the reaction site in the acetophenone.
GLC analyses were carried out on Chrom-5 device
equipped with flame-ionization detector, glass column
1200´3 mm, stationary phase SE-30 (5%) on a carrier
Inerton AW-DMCS (0.100–0.125 mm). TLC was
performed on Silufol plates, development with ninhydrine
The catalytic activity of crown ethers VII and X as
compared to that of crown ether IX, and that of compound
XIII relative to the activity of azacrown ether XII is
1
.5–2 times greater whereas the capability to asym-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

276
LUK’YANENKO et al.
solution in ethyl ether, and also glass plates with fixed
layer of neutral aluminum oxide (L 5/40) were used,
development in iodine vapor. The preparative liquid
chromatography was carried out on glass columns packed
with silica gel (L 40/100) or neutral aluminum oxide
stirring 1.0 g (8.2 mmol) of tetrol I or was added dropwise
a solution of 1.6 g (7.9 mmol) of diamine II in 5 ml of
anhydrous dioxane, and the stirring was continued for
1 h at 18–20°Ñ. To the mixture thus obtained was added
dropwise a solution of 13.8 g (35 mmol) of tosylate III in
2
5 ml of anhydrous dioxane, the temperature was raised
(L 40/250).
to 90–95°Ñ, and the stirring was continued for 16 h. The
reaction mixture cooled to 18–20°Ñ was poured by
portions to stirred ice water (50 ml), and the reaction
products were extracted into chloroform (3´50 ml). The
combined extracts were dried over Na SO , the solvent
was removed at a reduced pressure. The individual
podands IV and V were isolated as colorless oily
substances by column chromatography on neutral
aluminum oxide, eluent chloroform–benzene–methanol–
propanol, 8:3:0.3:0.3.
(
2S,3S)-1,2,3,4-Butanetetrol I and 1-benzyloxy-8-
tosyloxy-3,6-dioxaoctane III were prepared as described
before [10, 16].
(
4S,5S)-4,5-Bis(aminomethyl)-2-tert-butyl-2-
methyl-1,3-dioxolane (II). To a solution of 10.2 g
0.6 mol) of ammonia and 0.2 g (8.7 mmol) of sodium
metal in 100 ml of anhydrous methanol was added 28.8 g
0.1 mol) of diethyl (4R,5R)-2-tert-butyl-2-methyl-1,3-
2
4
(
(
dioxolane-4,5-dicarboxylate [11]. The mixture was stirred
for 3 h at 18–20°Ñ and left overnight. Then the reaction
mixture was evaporated by half, the precipitate was
filtered off and recrystallized from 40 ml of anhydrous
methanol. Yield of (4R,5R)-2-tert-butyl-2-methyl-1,3-
dioxolane-4,5-dicarboxamide 17.5 g (76%), colorless
crystals, mp 148–149°Ñ, [a] 11.1° (c 1.0, C H OH).
H NMR spectrum, d, ppm: 0.98 s (9H, t-Bu), 1.32 s
3H, CH ), 4.29 q (2H, CH), 7.10 s (2H, NH), 7.28 s
2H, NH). Found, %: C 52.19; H 7.92; N 12.21. M 230.
(
13S,14S)-13,14-Bis(2-{2-[2-(benzyloxy)-
e t h o x y ] e t h o x y } e t h o x y ) - 1 , 2 6 - d i p h e n y l -
2,5,8,11,16,19,22,25-octaoxahexacosane (IV). Yield
5.1 g (62%), [a]2 –6.0° (c 4.0, C H OH). H NMR
0
1
D
2
5
spectrum, d, ppm: 3.52–3.68 m (52H, CH ), 3.70–3.85 m
(2H, CH), 4.49 s (8H, CH Ph), 7.19–7.31 m (20H, Ph).
Found, %: C 66.60; H 8.23. M 1010. C H O .
2
2
0
D
2
5
2
1
+
5
6
82 16
(
(
Calculated, %: C 66.52; H 8.17. M 1011.17.
3
+
N,N-Bis(2-{2-[2-(benzyloxy)ethoxy]ethoxy}-
ethyl)-N-{[(4S,5S)-5-[2-(2-{2-[2-(benzyloxy)-
ethoxy]ethoxy}ethyl)-12-phenyl-5,8,11-trioxa-2-
C H N O . Calculated, %: C 52.16; H 7.88; N 12.17.
1
0
18
2
4
M 230.26.
To a dispersion of 5.6 g (148 mmol) of lithium aluminum
hydride in 100 ml of anhydrous THF under argon
atmosphere at vigorous stirring was added by small
portions 15.6 g (68 mmol) of (4R,5R)-2-tert-butyl-2-
methyl-1,3-dioxolane-4,5-dicarboxamide, the stirring was
continued for 2 h, then the temperature was raised to
boiling, and the mixture was heated at reflux for 8 h and
left overnight. Then at stirring while cooling with an ice
bath was added dropwise 5.6 ml of ice water, the
precipitate was filtered off, treated with boiling THF (3¥
azadodec-1-yl]-2-(tert-butyl)-2-methyl-1,3-dioxolan-
20
4-yl]methyl}amine (V). Yield 6.2 g (72%), [a]D -3.9°
1
(c 5.0, C2H5OH). H NMR spectrum, d, ppm: 0.89 s
(9H, t-Bu), 1.19 s (3H, CH3), 2.64–2.81m (12H, NCH2),
3.42–3.58 m (40H, OCH2), 3.60–3.82 m (2H, CH),
4.48 s (8H, CH2Ph), 7.18–7.29 m (20H, Ph). Found, %:
+
C 68.28; H 8.61; N 2.63. M 1090. C62H94N2O14.
Calculated, %: C 68.23; H 8.68; N 2.57. M 1091.43.
Reaction of ethylmagnesium bromide with
benzaldehyde and acetophenone in the presence
of chiral ligands. Asolution of 0.5 mmol of a ligand in 5
ml of anhydrous toluene preliminary saturated with
nitrogen was added to 0.24 g (10 mmol) of magnesium
turnings activated with iodine vapour. To this mixture was
added 0.22 g (2 mmol) of freshly distilled ethyl bromide,
and the mixture was stirred at 18–20°Ñ till the reaction
started (as was seen from the darkening of the metal
surface). Then a mixture of 0.87 g (8 mmol) of ethyl
bromide and 0.53 g (5 mmol) of benzaldehyde or 0.6 g (5
mmol) of acetophenone in 20 ml of anhydrous toluene
was added dropwise within 0.5 h. The stirring under
nitrogen atmosphere was continued till complete
conversion of the substrate (GLC monitoring). The
7
5 ml), the extract was combined with the filtrate, the
solution was dried on NaOH, THF was distilled off at
reduced pressure, and the residue was distilled in a
vacuum. Yield of diamine II 10.1 g (74%), bp. 90–91°Ñ
0
1
(
2 mm Hg), [a] 2 2.6° (c 2.5, C H OH). H NMR
D 2 5
spectrum, d, ppm: 0.92 s (9H, t-Bu), 1.22 s (3H, CH3),
2
3
.40 br.s (4H, NH ), 2.68–2.79 m (4H, NCH ), 3.47–
2
2
.80 m (2H, CH). Found, %: C 59.41; H 10.94; N 13.81.
+
M 202. C H N O . Calculated, %: C 59.37; H 10.96;
1
0
22
2
2
N 13.85. M 202.30.
Podands IV and V. To a dispersion of 1.9 g (79 mmol)
of sodium hydride in 20 ml of anhydrous dioxane was
added in small portions under argon atmosphere while
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 2 2004

STEREOSELECTIVITY OF GRIGNARD REACTION
277
reaction mixture was treated with a saturated solution of
ammonium chloride, the organic layer was separated, and
the water layer was extracted with ether (3´10 ml).
The ether extracts were combined with the toluene
solution, the solution obtained was washed in succession
with a saturated solution of sodium thiosulfate, with 10%
solution of sodium hydrogen carbonate, and with a little
water till neutral reaction. The solution was then dried
ner, M.R.W., Synthesis, 1993, p. 141; Sawamura, M.,
Nakayama, Y., Tang, W.-M., and Ito, J. , J. Org. Chem.,
1
996, vol. 61, p. 9090; Toke, L., Bako, P., Keseru, G. M.,
Albert, M., and Fenichel, L., Tetrahedron, 1998, vol. 54, p.
13; Bako, P., Bajor, Z., and Toke, L., J. Chem. Soc., Perkin
2
Trans. I, 1999, p. 3651; Bako, T., Bako, P., Szollosy, A.,
Czugler, M., Keglevich, G., and Toke, L., Tetrahedron
Asymmetry, 2002, vol. 13, p. 203.
. Bako, P., Czinege, E., Bako, T., Czugler, M., and Toke, L.,
Tetrahedron Asymmetry, 1999, vol. 10, p. 4539.
5
with MgSO , the solvents were distilled off at the
4
atmospheric pressure, and the residue was subjected to
column chromatography on silica gel, eluent pentane-
ethyl ether, 5:2. Thus a mixture of enantiomeric alcohols
6. Jansen, J.F.G.A. and Feringa, B.L., J. Org. Chem., 1990,
vol. 55, p. 4168; Stock, H.T. and Kellog, R.M., Abstracts of
Papers, 8th Int. Symp. Homogeneous Catalyse,
Amsterdam, 1992, p. 275.
was isolated, and their [a]2 was measured (see table).
0
D
7
8
9
. Tamai,Y., Hattori, T., Date, M., Koike, S., Kamikubo,Y.,Aki-
yama, M., Seino, K., Takayama, H., Oyama, T., and Miya-
no, S., J. Chem. Soc., Perkin, Trans. I, 1999, p. 1685.
. Bogatskii, A.V., Chumachenko, T.K., Luk’yanenko, N.G.,
Lyamtseva, L.N., and Starovoit, I.A., Dokl. Akad. Nauk
SSSR, 1980, vol. 251, p. 113.
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