Lithium perchlorate diethyl ether solution: A highly efficient media for the abramov reaction

Article abstract of DOI:10.1080/10426500307904

The α-hydroxy phosphonates are readily prepared by treating aromatic or aliphatic aldehydes and ketones with trialkylphosphite in the presence of trimethylsilylchloride in a very short time and in almost quantitative yields.

Full text of DOI:10.1080/10426500307904

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Phosphorus, Sulfur, and Silicon and the Related
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Lithium Perchlorate Diethyl Ether Solution: A Highly
Efficient Media for the Abramov Reaction
Najmedin Azizi a & Mohammad R. Saidi a
a Sharif University of Technology , Tehran, Iran
Published online: 27 Oct 2010.
To cite this article: Najmedin Azizi & Mohammad R. Saidi (2003) Lithium Perchlorate Diethyl Ether Solution: A Highly
Efficient Media for the Abramov Reaction, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:6, 1255-1259, DOI:
10.1080/10426500307904
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Phosphorus, Sulfur, and Silicon, 178:1255–1259, 2003
C
Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print
DOI: 10.1080/10426500390200530
LITHIUM PERCHLORATE DIETHYL ETHER
SOLUTION: A HIGHLY EFFICIENT MEDIA FOR THE
ABRAMOV REACTION
Najmedin Azizi and Mohammad R. Saidi
Sharif University of Technology, Tehran, Iran
(Received October 22, 2002; accepted November 19, 2002)
The -hydroxy phosphonates are readily prepared by treating aromatic
or aliphatic aldehydes and ketones with trialkylphosphite in the pres-
ence of trimethylsilylchloride in a very short time and in almost quan-
titative yields.
Keywords: Abramov reaction; -hydroxy phosphonates; lithium
perchlorate
Phosphonic acids and their phosphonate derivatives are of great inter-
est in the literature of organic chemistry due to their biological activity.1
They are employed in synthetic operations leading to carbon-carbon
bond formation2 and as transition state analogues in the production of
antibody catalyst for a wide variety of reactions.3 -Hydroxy phospho-
nates, specially enantiomerically pure -functionalized phosphonates,4
have been used for generating -substituted phosphonates such as
-halophosphonates, synthesis of halosubstituted alkenes, and alkynes
which are important intermediates in organic synthesis,5,6 preparation
of -keto phosphonates,7 synthesis of 1,2-diketons from acyl chlorides,
for preparation of -aminophosphonates and widely used for pharma-
ceutical applications.8 A number of synthetic methods for the prepara-
tion of -hyroxyphosphonates have been reported during the past two
decades.3,4,8 But these methods have the disadvantage of long reaction
time or difficult conditions.
We are grateful to the Ministry of Science, Research and Technology for financial sup-
port of this research. We also thank Volkswagen-Stiftung, Federal Republic of Germany
for financial support toward the purchase of equipment and chemicals.
Address correspondence to Mohammad R. Saidi, Department of Chemistry, Sharif
University of Technology, PO Box 11365-9516, Tehran, Iran.
1255

1256
N. Azizi and M. R. Saidi
RESULTS AND DISCUSSION
During the course of our effort using a 5 M ethereal solution of
lithium perchlorate, LPDE, for one-pot three-components method for
aminoalkylation of aldehydes with different nucleophiles such as
organolithium, organomagnesium, organosilicon, and functionalized
organozinc compounds,9 we found that the reaction of aldehydes or ke-
tones with trialkylphosphite in the presence of trimethylsilylchloride,
TMSCl, proceeded smoothly at ambient temperature to give -hydroxy
phosphonates with very high yields in a few minutes.
By the addition of aldehyde 1 (1.0 equiv.), to an excess of freshly dis-
tilled trialkylphosphite (1.25 equiv.) and 1 equiv. of TMSCl in a concen-
trated ethereal solution of lithium perchlorate, -hyroxyphosphonate
was formed within 5 min. The transformation was carried out at
room temperature with easy work-up and without any by-products.
This procedure has been followed for the preparation of all -hyroxy-
phosphonates listed in Table I. Although the lithium perchlorate me-
diated aminoalkylation of enolizable aldehydes proceeds in low yields,
and the aminoalkylation reaction of ketones has not been reported in
ethereal solution of lithium perchlorate, this procedure can be applied
for both enolizable (entry 11–14, Table I) and nonenolizable aldehydes
and ketones (entry 15–16, Table I), Scheme 1. The crude products were
obtained in a high purity.
SCHEME 1
By using chiral aldehyde such as (1R)-(-)-myrtenal, -hyroxyphos-
phonate of (1R)-(-)-myrtenal (entry 17, Table I) was produced with the
1
same procedure. The H NMR spectra of the crude product showed a
mixture of two diastereomers for 3s with the ratio of 82 to18.11 The con-
figuration and the ratio of the major diasereomer was determined by
1H NMR spectra of the crude product and comparison of the chemical
shift and coupling constant of the proton attached to the carbon bearing
the phosphonate group with similar compounds reported in the litera-
ture. Each diasereomer shows a doublet with different chemical shift
and coupling constant. The upfield doublet was assigned to the major
diasereomer (R, S)-3.

Lithium Perchlorate Diethyl Ether Solution
1257
TABLE I -Hydroxyphosphonates Obtained from the Abramov
Reaction in Ethereal Solution of Lithium Perchloratea

1258
N. Azizi and M. R. Saidi
EXPERIMENTAL
All products were identified with their NMR and IR spectroscopic data.
The starting materials were used as received without further purifica-
tion. Trimethy phosphite and triethyl phosphite were distilled before
use. Lithium perchlorate was dried according to the procedure described
in the literature.9a
General Procedure for the Preparation
of -Hyroxyphosphonates
The aldehyde (2 mmol) and 3 ml of 5 M LiClO4 in diethyl ether were
placed in a 25 ml flask under argon and freshly distilled trialkyl phos-
phite (2/5 mmol) and TMSCl (2 mmol) were added via a syringe and the
mixture was stirred for 5 min. Then, water (15 ml) and dichloromethane
(15 ml) were added. The organic phase was separated and washed with
water, dried with Na2SO4, and the solvent was removed in a rotary
evaporator. All products gave satisfactory spectral data in accordance
to the proposed structures and with those reported in the literature.4,8
Spectral data of the new compounds are: 3a, 1H NMR, H, (CDCl3,
500 MHz), 3.58 (d, 3H, J = 10.3 Hz), 3.63 (d, 3H, J = 10.3 Hz), 5.03
(d, 1H, J = 13.2 Hz), 6.00 (br s, OH), 7.28–7.47 (m, 5H); 13C NMR,
C, (CDCl3, 125 MHz), 53.7 (d, J = 7.5 Hz), 54.2 (d, J = 7.5 Hz),
CP
CP
69.1 (d, J = 164 Hz), 128.8, 129.4, 131.1, 133.8 (d, J = 2.9 Hz); IR
CP
CP
(KBr); 3430, 1030. 3i, IR (KBr): 3430 (br, OH), 1030 cm 1; H NMR,
H, (CDCl3, 500 MHz), 3.60–3.69 (m, 6H), 5.09 (d, 1H, J = 13.4 Hz), 6.2
(br s, OH), 7.42 (d, 2H, J = 8.5 Hz), 7.48 (d, 2H, J = 8.5 Hz); 13C NMR,
C, (CDCl3, 125 MHz), 53.7 (d, J = 7.1 Hz), 54.2 (d, J = 7.5 Hz),
1
CP
CP
69.1 (d, J = 161.1 Hz), 128.8, 129.4, 133.1 (d, J = 3.9 Hz), 138.2; IR
CP
CP
(KBr); 3423, 1253, 1030. 3p, IR (KBr): 3430 (braod, OH), 1030 cm 1; 1H
NMR, H, (CDCl3, 500 MHz), 1.14–1.74 (m, 10H), 3.66 (d, 6H, J = 10.1
Hz), 5.22 (br s, 1H, OH); 13C NMR, C, (CDCl3, 125 MHz), 20.4 (d,
J
= 11.5 Hz), 27.3, 32.0 (d, J = 2.7 Hz), 53.7 (d, J = 7.5 Hz), 71.0
CP
CP
CP
(d, J = 164.2 Hz). 3s, White solid, mp = 98–100 C; IR (nujol): 3423
CP
(br, OH), 1661, 1053 cm 1; 1H NMR, H, (CDCl3, 500 MHz) for the ma-
jor diastereoisomer, 0.80 (s, 3H), 1.07 (d, 1H, J = 8.3 Hz), 1.25 (s, 3H),
2.04–2.36 (m, 5H), 3.61 (d, 3H, J = 11.4 Hz), 3.67 (d, 3H, J = 11.1 Hz)
4.28 (d, 1H, J = 13.6 Hz), 5.45 (br s, 1H), 5.56 (s, 1H); 13C NMR,
,
C
(CDCl3, 125 MHz), for the major diastereoisomer, 21.8, 26.8, 31.8, 32.2,
38.2, 40.9, 43.2, 53.3 (d, J = 7.3 Hz), 53.6 (d, J = 7.1 Hz), 70.3 (d,
CP
CP
J
= 161.7 Hz), 120.5 (d, J = 12.5 Hz), 145.3 (d, J = 2.6 Hz). Anal.
CP
CP
CP
Calcd. for C12H21O4P: C, 55.37; H, 8.13. Found: C, 55.65; H, 8.25.

Lithium Perchlorate Diethyl Ether Solution
1259
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