Reaction of acetyl- and alkylideneglycosylamines with diphenylphosphinous acid

Article abstract of DOI:10.1134/s1070363208020059

An original method of synthesis of optically active α-aminophosphoryl compounds containing a carbohydrate residue is proposed.

Full text of DOI:10.1134/s1070363208020059

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 2, pp. 185 191.
Original Russian Text A.M. Koroteev, A.A. Bobrikova, M.P. Koroteev, K.A. Lysenko, E.E. Nifant’ev, 2008, published in Zhurnal Obshchei Khimii,
2008, Vol. 78, No. 2, pp. 202 209.
Pleiades Publishing, Ltd., 2008.
Reaction of Acetyl- and Alkylideneglycosylamines
with Diphenylphosphinous Acid
A. M. Koroteeva, A. A. Bobrikovaa, M. P. Koroteeva,
K. A. Lysenkob, and E. E. Nifant’eva
a Moscow Pedagogical State University,
Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: nastenka-bobrik@yandex.ru
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Received October 10, 2007
Abstract An original method of synthesis of optically active -aminophosphoryl compounds containing a
carbohydrate residue is proposed.
DOI: 10.1134/S1070363208020059
The Kabachnik Fields reaction discovered in 1952
still remains an effective method of phosphorus
carbon bond formation [1]. Despite the long-standing
researcher’s interest in methods of synthesis and
properties of -aminophosphoryl compounds, a lot of
problems in this field of organophosphorus chemistry
have still to be solved. Possibilities for modification
aimed at obtaining -aminophosphoryl compounds on
the basis of new substrates, first of all of natural
origin, are far from being exhausted. Development of
new convenient procedures for synthesis of such
derivatives under mild conditions and in high yields
still remains an urgent problem. It is noteworthy
glycosylamines have never been introduced in the
Kabachnik Fields reaction. At the same time, mutaro-
tation of these compounds involves intermediate
formation of the imino form which is expected to
react with hydrophosphoryl compounds.
tion of anilines derived from protected monosac-
charides. Here we present the first results of this
research.
As substrates for phosphorylation we chose ac-
cessible triose, pentose, and hexose amino derivatives
representing both open-chain and cyclic (pyranose and
furanose) monosaccharides. Full protection of hyd-
roxy groups in the carbohydrate fragment of the
anilide molecules excluded their furanization.
Throughout the investigation the nitrogen-containing
part of the anilines and phosphorylating agent were
not varied. Such set of N-glycosides allowed us to
study the reactivity of the anilines in the non-classical
variant of the Kabachnik Fields reaction as a function
of the structure of their carbohydrate moiety and to
draw tentative conclusions of the reaction scheme.
As thesimplest carbohydrate-containing azomethine
we used N-[(2,2-dimethyl-1,3-dioxolan-4-yl)methyle-
ne]aniline (II). Its synthesis has been described by
Yoshimura et al. [6] who found that this compound is
unreasonable to isolate by distillation or crystalliza-
tion because the conversion of the imino to amino
form. Therefore, we applied compound II without
isolation. Its formation was detected by TLC, after
which the compound was immediately involved into
the phosphorylation reaction. Glycerose I was syn-
thesized alongside the procedure in [7].
We have studied the reaction of unprotected mono-
and disaccharide anilides with dipenylphosphinous
acid. It has been shown that the phosphorus-contain-
ing function adds to the glycoside center to form
-amino-tert-phosphine oxides. The process is com-
plicated by furanization of the carbohydrate fragment
[2]. However, provided the carbohydrate fragment has
been preserved, the reaction leads to -aminophos-
phoryl derivatives of carbohydrates, which represent
a wide and chemically diverse class of compounds.
Some of such compounds possess important and
useful properties, e.g., exhibit high and diverse
physiological activity [3 5]. Therefore, we extended
investigations in this area and turned to phosphoryla-
We found that reaction of compound II with di-
penylphosphinous acid (III) proceeds under fairly
mild conditions (at 20 C) and is complete in 2 3 h.
185

186
KOROTEEV et al.
C14
C15
C16
C13
C7
C6
O6
C17
O2
N1
C12
C8
C3
C2
O5
O3
C1
C9
O1
C5
O4
C10
C4
C11
O7
1
5
1
6
Fig. 1. General view of molecule V with thermal ellipsoids drawn at the 50% probability level. Bond lengths ( ): O
C
C
1
5
1
12
1
1
2
2
3
3
4
4
1.452(2), O C 1.422(2), N
C
1
1.392(2), N C 1.412(2), O C 1.436(2), C O 1.438(2), C O 1.437(2), and O
5
1
12
1
1
1.202(2); angles (deg): C
O
C
111.75(14) and C
N C 121.23(15).
1-deoxy-2,3-O-isopropylidene-1-(diphenylphosphi-
noyl)-1-(phenylamino)-D-glycerol (IV) crystallized
spontaneously from the reaction mixture and could be
isolated in a high yield (67%) (Scheme 1).
Scheme 1.
H
O
Ph
Ph
O
H3C CH3
P
C H
H3C CH3
O O
H
H
III
NH2Ph
HOH
O O
O CH
O CH2
H3C
H3C
H2C C C N Ph
H
H2C C C=N Ph
H H
Ph
P
Ph
O
I
II
IV
This result is quite expectable, because the parent
azomethine derived from triose is incapable of
mutarotation and consists of 100% linear (syn and
anti) forms of the free Shiff base. It readily undergoes
the classical addition of the phosphorus compound at
the C=N double bond (the Pudovik variant of the
Kabachnik Fields reaction [8, 9]).
cule V in crystal is a anomer. The pyranose ring has
4
a C1 conformation, and the C1 and C4 atoms deviate
from the C2O1C3C5 ring plane by 0.73 and 0.69
,
respectively. The phenyl group is planar, the sum of
all bond angles in it is 358.4 . The dihedral angle
between the NHPh fragment and the ring plane is
129.8 . The intermolecular hydrogen bonds N1
H1NO6 [x + 1, y, z] in the crystal join molecules into
chains running along the crystallographic axis a.
The pentose derivative involved in the reaction was
2,3,4-tri-O-acetyl-1-deoxy-1-(phenylamino)-D-xylo-
pyranose (V) prepared alongside the procedure in [10,
11]. In our present work we determined its structure
by X-ray diffraction analysis (Fig. 1), which was
necessary for structural assessment of the most stable
prevailing isomer in the reaction mixture. Under the
reaction conditions, compound V can undergo mutaro-
tation.
We established that the reaction of pyranosylaniline
V with acid III proceeds by Scheme 2.
The reaction is complete in 18 20 h at 20 C.
Adding pyridine to the reaction mixture almost halves
the reaction time, which can be explained in terms of
both accelerated mutarotation of the carbohydrate
component mutarotation and accelerated isomerization
of dipenylphosphinous acid into a reactve P(III) form.
As follows from the X-ray diffraction data, mole-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008

REACTION OF ACETYL- AND ALKYLIDENEGLYCOSYLAMINES
187
Scheme 2.
Ph
O
Ph
Ph
P
HN
O
C
H
H
AcO
AcO
OAc
H
NH Ph + III
AcO
H
OAc
OAc
V
CH2OH
VI
The yield of 2,3,4-tri-O-acetyl-1-deoxy-1-(diphe-
nylphosphinoyl)-1-(phenylamino)-D-xylitol (VI) after
chromatographic purification was 48.5%. Thus, the
necessity of preliminary mutarotation of glycosyl-
amine (conversion to the imino form) stipulates a
longer reaction time as compared with the synthesis of
-amino-tert-phosphine oxide IV, all other reaction
conditions being the same.
Another structurally similar substrate but derived
from hexose, viz. 2,3,4,6-tetra-O-acetyl-1-deoxy-1-
(phenylamino)-D-glucopyranose (VII) [10, 11], does
not react with dipenylphosphinous acid at all without
heating and adding a catalyst. This reaction could only
be accomplished in the presence of pyridine or
cadmium iodide under heating at 55 60 C for 10
12 h. The yield of -amino-tert-phosphine oxide VIII
was 30% or lower (Scheme 3).
Scheme 3.
Ph
O
Ph
Ph
HN
P
CH
OAc
OAc
H
H
O
AcO
H
AcO
NH Ph + III
OAc
AcO
OAc
VII
H
OAc
CH2OAc
VIII
Such a difference in the reactivity of aniline deriv-
atives of pentose and hexose seems surprising. Note
that the similarity of the steric structures of -ano-
meric aniline derivatives of hexopyranose and xylo-
pyranose is obvious from a comparison with data in
[12]. The difference in the structures of -glucopyra-
nosylanilines derived from D-xylose and D-glucose
consists in that the C5 atom of the pyranose ring in
the latter bears an acetoxymethyl substituent. This
substituent can pose steric hindrance only in a cyclic
glucosylamine, since in the imino form it resides at
the periphery of the reacting molecule. Probably, the
lower reactivity of compound VII is associated with
restricted ring chain isomerization as compared with
the xylopyranose analog or with a different reaction
mechanism: The process may involve substitution of
the C O fragment in the cyclic form of glycosylamine
VII by a phosphinoyl group.
The next step of the study is investigation of the
reaction of dipenylphosphinous acid with glycosyl-
amines derived from D-mannose ketal, 1-deoxy-2,3;
5,6-di-O-isopropylidene-1-(phenylamino)- -D-manno-
furanose (IX) and 2,3;5,6-di-O-cyclohexylidene-1-
deoxy-1-(phenylamino)- -D-mannofuranose (X).
A
preliminary communication concerning this part of
investigation has been published in [2]. In the present
work we studied the crystal structure of compound IX
by X-ray diffraction (see table).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008

188
KOROTEEV et al.
C9
O6
C12
C10
C6
O2
C11
C18
C7
C17
C5
O5
C13
O3
C16
O1
C8
C4
N1
C3
C2
C1
C14
2
1
2
1
Fig. 2. General view of molecule IX with thermal ellipsoids drawn at the 50% probability level. Bond lengths ( ): O
C
C
2
7
1
6
4
6
1
1
3
7
3
3
1
13
1.424(4), O
C
C
1.437(4), O
C
1.436(4), O
C
1.461(4), O
C
1.430(5), O
10
C
1.438(4), N
C
1.400(4), N
O
6
10
5
5
5
2
2
7
1.412(5), O
1.425(5), O C 1.428(5), O C 1.435(4), and O
C
1.458(4); bond angles (deg): C
C 106.4(3),
4
1
1
7
3
3
13
1
1
10
6
6
5
5
10
C
O
C
104.9(2), C
O
C
107.1(3), C
N
C
121.4(3), C
O C 106.5(3), and C O C
109.7(3).
According to the X-ray diffraction data, compound
IX is a anomer containing the mannose residue in
the furanose form O1ð with the O1 atom deviating
Furanozides IX and X react with compound III in
even more rigid conditions ( 60 C, 23 27 h) with
pyridine as catalyst (Scheme 4).
from the mean C1C2C3C4 plane by 0.56
and two
dioxolane rings in the envelope conformation with the
O6 and C7 atoms deviating from the corresponding
ring planes by 0.49 and 0.50 , respectively (Fig. 2).
The dihedral angle between the furanose and dioxo-
lane ring planes is 116.3 . The phenyl ring is planar.
Like in the crystal of V, molecules IX form
N1 H1NO5 [x, y + 1, z] hydrogen bonds which join
the molecules into chains running along the crystal-
lographic axis a.
The presence in ketals IX and X of additional
cyclic structures undoubtedly decelerates mutarotation
and probably retards sterically the attack of the P(III)
reagent. The different size of the protective groups in
IX and X affects to a certain degree the phosphoryla-
tion rate: The reaction time of the cyclohexylidene
derivative is longer by 5 h as compared with the iso-
propylidene derivative. Products XI and XII were
isolated by column chromatography on silica gel. The
Details of X-ray diffraction experiment and crystal data for compounds V and IX
Parameters
V
IX
Parameters
V
IX
Brutto formula
Molecular weight
Difraktometr
C17H21NO7
351.35
Bruker SMART
APEX II CCD
100(2)
C18H25NO5
335.39
Bruker SMART
1000 CCD
120(2)
Monoclynic
P21
Scanning
, deg
1.97 28.99
99.8
1.57 27.00
99.2
Percentag of
possible reflections
measured (%)
Number of
measured
Temperature, K
Crystal system
Space group, Z
Rhombic
P212121
10091
5725
a,
b,
c,
, deg
V,
Z(Z )
F(000)
dcalc
7.7687(9)
13.0713(16)
16.900(3)
23.089(19)
6.751(6)
12.326(10)
112.572(16)
1774(3)
reflections
Number of unique 2596 [0.0332] 2114[Rint 0.0485]
reflections
Number of refined
parameters
R(Fhkl): R1
wR2
233
221
1716.2(4)
4(1)
744
1.360
1.06
2(1)
720
1.256
0.91
0.0340
0.0878
1.076
0.0516
0.1149
1.003
1
,
g cm
GOF
Linear absorption,
, cm
,
,
min
0.28, 0.22
0.347, 0.233
max
1
3
e
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008

REACTION OF ACETYL- AND ALKYLIDENEGLYCOSYLAMINES
189
Scheme 4.
Ph
O
Ph
Ph
Ph
HN
P
O
HN
CH
O
O
O
O
+ III
R
O
H
R
R
O
H
H
H
OH
O
R
CH2O
CH3
R =
C
C
(IX),
(X).
CH3
yields after purifications were 41 and 52%,
respectively.
nous acid probably occur nonstereospecifically and
afford mixtures of optical isomers. To conclude, we
thus proposed an unique synthetic approach to
-
The synthesized compounds were all characterized
aminophosphoryl compounds derived from glycosyl-
amines and synthesized a series of new -amino-tert-
phosphine oxides that contain a carbohydrate fragment
in their structures and hold promise in terms of
diverse physiological activity.
1
by TLC, H, 13C and 31P NMR spectroscopy and
elemental analysis (see Experimental).
Products VI, VIII, XI, and XII are light yellow
thick syrups, and compound IV is a powder with a
high melting point. On TLC plates the products give
slightly oblong spots with Rf 0.55 0.7. The 31P NMR
signals of the synthesized phosphine oxides appear at
EXPERIMENTAL
28 31 ppm; therewith, compounds IV, VI, XI, and
All experiments with P(III) reagents were carried
out under dry argon with solvents purified and dried
according to conventional procedures [13].
P
XII give by two signals, while compound VIII, only
one signal. Hence, the addition of the hydrophospho-
ryl compound proceeds mainly nonstereospecifically
to form a mixture of two optical isomers. The integral
The 31P NMR spectra were measured on a Bruker
WP-80 spectrometer at 32.4 MHz against external
1
intensity ratios of the H NMR signals of the protec-
1
reference 85% H3PO4. The H NMR spectra were
tive groups and aromatic and carbohydrate fragments
of compounds IV, VI, VIII, XI and XII confirm their
structures. All proton signals display expected multi-
plicities and spin spin coupling constants, e.g. the
2JHP for protons on C1 is about 12 Hz. In the 13C
NMR spectra, the signals of carbon atoms proximate
to phosphorus are split due to C P spin spin coupling.
For example, the C1 signals of X and XI are doublets
measured a Bruker H-250 spectrometer at 250 MHz
against residual proton signals of the deuterated
solvent. The 13C NMR spectra were measured on a
Bruker AMX-400 at 100.61 MHz against residual
proton signals of the deuterated solvent.
Thin-layer chromatography was carried out on
Silufol UV-254 plates, development by calcination.
Adsorption chromatography was carried out on a
silica gel L 40 100 m column, eluents benzene
acetonitrile hexane, 4:2:1 (A) and benzene dioxane,
3:1 (B).
in the characteristic region
50 52 ppm (JCP 77.8
and 77.6 Hz, respectively). TChe C2 signal of the car-
bohydrate fragments in X and XI, too, are split due to
C P spin spin coupling (2JCP 8.6 and 9.6 Hz,
respectively).
The X-ray diffraction study was carried out on a
Thus, glycosylamines derived from acetylated and
ketalated trioses, pentoses, and hexoses are much less
active in the Kabachnik Fields reaction as compared
with glycosamines derived from free monosaccharides,
and protected monoses undergo no furanization on
phosphorylation. The reaction with dipenylphosphi-
Bruker Smart diffractometer at 100 K (MoK radia-
tion, 2
52.00 ). The structure was solved by the
max
direct method, all non-hydrogen atoms were located
in difference Fourier synthesis maps and refined
anisotropically on F2hkl. Hydrogen atoms were located
in difference Fourier synthesis maps and refined iso-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008

190
KOROTEEV et al.
5.49 Hz); 5.32 m (1H, C3H); 5.54 m [1H, C1H, 3JH,H
2
tropically in the rigid body approximation. All cal-
culations were performed using the SHELXTL 5.10
program suite [14].
2
3
8.53 Hz, JHP 12.05 Hz, JH,H(NH) 7.67 Hz]; 6.36 m
3
3
5
5
(1H, OH, JH,H 2.59 Hz, JH,H 2.56 Hz); aniline
3
1-Deoxy-2,3-O-isopropylidene-1-(diphenylphos-
phinoyl)-1-(phenylamino)-D-glycerol (IV). Aniline,
0.93 g, was added with stirring at room temperature
under argon to a solution of 1.3 g of 2,3-O-isopropyl-
idene-D-glycerose in benzene. After 30 min, 2.02 g of
dipenylphosphinous acid was added to the mixture,
and stirring was continued for 2.5 h. The precipitate
that formed was filtered off, washed with ether, and
dried in a vacuum. Yield 2.45 g (67%). Light yellow
1
fragment, 5.92 m (1H, NH, JH,H 7.67 Hz), 6.88 d
(2H, C2H, C6H, JHH 7.69 Hz); 7.05 t (1H, C4H,
3
3
JHH 6.67 Hz); 7.26 d.d (2H, C3H, C5H, JHH
3
3
3
4
3
2,6
6.67 Hz, JHH 7.67 Hz); diphenylphosphinoyl frag-
ment, 7.47 m (3H, C3H, C4H, C5H); 7.63 m (3H, C3 H,
C4 H, C5 H) 7.84 m (2H, C2H, C6H, JHP 11.10 Hz),
3
8.11 m (2H, C2H, C6H, JHP 11.10 Hz). 13C NMR
3
spectrum (acetone-d6), C, ppm: carbohydrate frag-
powder, mp 208 210 C. 31P NMR spectrum (acetone-
d6), P, ppm: 28.95 (50%), 29.2 (50%). 1H NMR spec-
trum (acetone-d6) , ppm: glycerol fragment, 2.03
2.08 m (6H, CH3); 3.6 3.8 m (2H, C3H), 4.10 m (1H,
1
ment, 19.7 21.6 m [H3C C(O)]; 51.1 d (C1, JCP
2
80.49 Hz); 57.8 (C5); 62.1 (C4); 67.4 d (C2, JCP
3
24.15 Hz); 69.4 d (C3, JCP 13.08 Hz); 142.8 [O4
C2H), 6. 35 m (1H, C1H, JHP 16.05 Hz); aniline
2
C(O) CH3]; 161.5 [O3 C(O) CH3]; 169.7 [O2 C(O)
fragment, 6.30 br.s (1H, NH), 6.66 d (2H, C2H, C6H,
CH3]; aniline fragment, 110.5 (C2, C6); 114.4 (C4);
3
3
JHH 7.56 Hz); 7.05 t (1H, C4H, JHH 8.4 Hz);
3
128.6 (C3, C5); 146.2 d (C1, JCP 5.5 Hz); diphenyl-
3
3
7.41 d.d (2H, C3H, C5H, 3JHH 8.4 Hz, 3JHH2,6 7.56
phosphinoyl fragment, 128.3 128.7 m (2C3, 2C5);
4
Hz); diphenylphosphinoyl fragment, 7.47 m (3H, C3H,
1
130.6 131.2 d (2C1, JCP 10.1 Hz); 131.5 132.3 m
C4H, C5H); 7.58 m (3H, C3 H, C4 H, C5 H) 7.83 m
(2C4, 2C2, 2C6). Found, %: C 62.79, 62.84; H 5.84,
5.85; N 2.54, 2.55; P 5.52, 5.53. C29H32NO8P. Cal-
culated, %: C 62.93; H 5.79; N 2.62; P 5.61.
(2H, C2H, C6H, JHP 10.96 Hz), 7.89 m (2H, C2H,
3
C6H, 3JHP 10.96 Hz). 13C NMR spectrum (DMSO-d6),
C, ppm: glycerol fragment, 26.2 27.1 m (H3C C
2,3,4,6-Tetra-O-acetyl-1-deoxy-1-(diphenylphos-
phinoyl)-1-(phenylamino)-D-glucitol (VIII). Dipe-
nylphosphinous acid, 0.4 g, and 2.5 ml of pyridine
(or 0.1 g of CdI2) were added under argon to a solu-
tion of 0.42 g of 2,3,4,6-tetra-O-acetyl-1-deoxy-1-
(phenylamino)-D-glucopyranose in 5 ml of chloroform.
The reaction mixture was heated at 55 60 C, stirred
for 12 h, diluted with 15 ml of ethanol, decolorized
by refluxing with 1 g of charcoal, filtered, concen-
trated in a vacuum, and passed through a column of
silica gel (eluent B). The fraction with Rf 0.55 0.6
CH3); 55.6 d (C1, JCP 74.8 Hz); 63.8 d (C3, JCP
1
3
5.2 Hz); 98.6 d (C2, 2JCP 8.7 Hz); 121.3 [O2 C(CH3)2
O3]; aniline fragment, 113.8 (C2, C6); 118.6 (C4);
128.6 (C3, C5); 132.4 d (C1, JCP 3.8 Hz); diphenyl-
3
phosphinoyl fragment, 128.6 129.2 m (2C3, 2C5);
130.8 131.9 m (2C1, 2C4, 2C2, 2C6). Found, %: C
70.84, 70.82; H 6.28, 6.32; N 2.98, 3.03; P 7.55, 7.58.
C24H26NO3P. Calculated, %: C 70.76; H 6.39; N 3.44;
P 7.62.
was collected. Yield 0.2 g (29.8%). Syrup. 31P NMR
2,3,4-Tri-O-acetyl-1-deoxy-1-(diphenylphos-
phinoyl)-1-(phenylamino)-D-xylitol (VI). Dioxane,
3 ml, was added with stirring under argon to a mix-
ture of 0.2 g of dipenylphosphinous acid and 0.32 g of
2,3,4-tri-O-acetyl-1-deoxy-1-(phenylamino)-D-xylo-
pyranose, and the mixture was left to stand for a day
at room temperature. After complete reaction, the
solution was concentrated and passed through a
column of silica gel (eluent B); the fraction with Rf
0.65 0.75 was collected. Yield 0.25 g (48.5%). Color-
1
spectrum (acetone-d6), P, ppm: 30.6. H NMR spec-
trum (acetone-d6), , ppm: carbohydrate fragment,
1.96 1.99 m (12H, CH3); 4.04 m (H, C6H); 4.09 m
(1H, C6 H); 4.20 m (1H, C5H); 4.80 m (1H, C4H);
4.93 m (1H, C3H); 5.23 m [1H, C1H, 3JH,H 5.12 Hz,
2
3
2JHP 12.08 Hz, JH,H(NH) 5.48 Hz]; 5.54 m (1H, C2H,
3
1
JH,H 5.12 Hz); 6.87 m (1H, OH); aniline fragment,
6.46 m (H, NH, JH,H 5.48 Hz), 7.27 d (2H, C2H,
3
1
C6H, JHH 8.41 Hz); 7.33 t (H, C4H, 3JHH 7.27 Hz);
3
less syrup. 31P NMR spectrum (acetone-d6), P, ppm:
27.6 (32%), 28.2 (68%). H NMR spectrum (acetone-
3
3
7.38 d.d (2H, C3H, C5H, JHH 7.27 Hz, JHH
3
3
1
4
2,6
d6), , ppm: carbohydrate fragment, 1.92 2.01 m (9H,
8.41 Hz); diphenylphosphinoyl fragment, 7.50 m (3H,
C3H, C4H, C5H); 7.60 m (3H, C3 H, C4 H, C5 H)
2
3
CH3); 3.74 m [H, C5H, JH,H 10.41 Hz, JH,H
5
4
3
3
5.49 Hz, JH,H(OH) 2.56 Hz]; 3.84 m [1H, C5 H, JH,H
3
7.85 m (2H, C2H, C6H, JHP 11.09 Hz), 8.12 m (2H,
5
3
3
3
C2H, C6H, JHP 11.09 Hz). 13C NMR spectrum
4
10.41 Hz, JH,H 5.49 Hz, JH,H(OH) 2.59 Hz]; 4.77 m
(1H, C2H, JH,H 8.53 Hz); 4.93 m (1H, C4H, JH,H
3
3
1
5
(acetone-d6), P, ppm: carbohydrate fragment, 13.6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008

REACTION OF ACETYL- AND ALKYLIDENEGLYCOSYLAMINES
191
[H3C C(O) O6]; 19.7 [H3C C(O) O2, H3C C(O) O3];
23.7 [H3C C(O) O4]; 61.8 d (C1, 1JCP 80.49 Hz); 66.7
[O5 C(CH2)5 O6]; aniline fragment, 112.2 (C2, C6);
116.0 (C4); 128.2 (C3, C5); 146.7 d (C1, 3JCP 3.1 Hz);
diphenylphosphinoyl fragment, 127.5 128.7 m (2C3,
2C5); 130.4 133.5 m (2C1, 2C4, 2C2, 2C6). Found, %:
C 70.15, 70.19; H 7.25, 7.22; N 2.13, 2.12; P 5.36,
5.29. C36H44NPO6. Calculated, %: C 70.02; H 7.13; N
2.27; P 5.02.
3
(C6); 67.5 (C5); 68.7 d (C3, JCP 5.8 Hz); 71.4 d (C2,
2JCP 8.5 Hz); 72.8 (C4); 169.3 [O6 C(O) CH3]; 169.6
[O3 C(O) CH3]; 169.8 [O2 C(O) CH3]; 170.0
[O4 C(O) CH3]; aniline fragment, 114.2 (C2, C6);
119.1 (C4); 128.6 (C3, C5); 132.5 d (C1, 3JCP 2.1 Hz);
diphenylphosphinoyl fragment, 128.5 129.0 m (2C3,
2C5); 131.0 131.5 m (2C1, 2C4, 2C2, 2C6). Found, %:
C 61.05, 61.10; H 5.79, 5.78; N 2.54, 2.52; P 4.59,
4.54. C34H38NO11P. Calculated, %: C 61.17; H 5.70;
N 2.62; P 4.65.
ACKNOWLEDGMENTS
This work was financially supported by the Prog-
ram of the President of the Russian Federation for
Support of Leading Russian Scientific Schools (grant
no. NSh-5515.2006.3).
tert-Phosphine oxides XI XII (general procedure).
A solution of 1-deoxy-2,3;5,6-di-O-isopropylidene-
(cyclohexylidene)-1-(phenylamino)- -D-mannofura-
nose, 0.05 mol, and 0.05 mol of dipenylphosphinous
acid in a mixture of 5 ml of chloroform and 3 ml of
pyridine was stirred under argon for 23 27 h at 60 C.
The solvent was then removed in a vacuum, and the
residue was purified by chromatography on silica gel
in system A. Products XI are XII were isolated as
yellow syrups crystallized with time, soluble in most
organic solvents, and isoluble in water.
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1-Deoxy-1-2,3;5,6-di-O-isopropylidene-1-(di-
phenylphosphinoyl)-1-(phenylamino)-D-mannitol
(XI). Yield 41%. Rf 0.66. 31P NMR spectrum
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(DMSO-d6), P, ppm: 29.5 (31.3%); 31.0 (68.7%).
13C NMR spectrum (DMSO-d6), C, ppm: carbohyd-
rate fragment, 25.3 27.3 m (H3C C CH3); 54.7 d
6. Yoshimura, J., Ohgo, Y., and Sato, T., J. Am. Chem.
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1
(C1, JCP 77.8 Hz); 66.4 (C6); 69.6 (C4); 74.9 d (C3,
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Commun., 1991, vol. 21, p. 151.
2
3JCP 5.4 Hz); 76.0 (C5); 80.2 d (C2, JCP 8.6 Hz);
108.2 [O2 C(CH3)2 O3]; 108.8 [O5 C(CH3)2 O6];
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Nauk SSSR, 1952, vol. 83, no. 5, p. 689.
aniline fragment, 112.8 (C2, C6); 116.5 (C4); 128.6
3
(C3, C5); 147.3 d (C1, JCP 3.5 Hz); diphenylphos-
9. Nifant’ev, E.E., Khimiya gidrofosforil’nykh soedinenii
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phinoyl fragment, 127.6 128.2 m (2C3, 2C5); 130.6
133.7 m (2C1, 2C4, 2C2, 2C6). Found, %: C 67.28,
67.29; H 6.57, 6.60; N 2.54, 2.55; P 5.89, 5.92.
C30H36NPO6. Calculated, %: C 67.16; H 6.53; N 2.62;
P 5.78.
10. Helferich, B. and Mitrowsky, A., Chem. Ber., 1952,
vol. 85, p. 1.
11. Onodera, K., Hirano, S., and Fukumi, H., Agr. Biol.
Chem., 1964, vol. 28(3), p. 173.
2,3;5,6-Di-O-cyclohexylidene-1-deoxy-1-(di-
phenylphosphinoyl)-1-(phenylamino)-D-mannitol
(XII). Yield 52%. Rf 0.85. 31P NMR spectrum
12. Metlitskikh, S.V., Koroteev, A.M., Koroteev, M.P.,
Shashkov, A.S., Korlyukov, A.A., Antipin, M.Yu.,
Stash, A.I., and Nifant’ev, E.E., Izv. Ross. Akad.
Nauk, Ser. Khim., 2005, no. 12, p. 2793.
(DMSO-d6), P, ppm: 28.4 (40.65%); 30.9 (59.35%).
13C NMR spectrum (DMSO-d6), C, ppm: carbohyd-
rate fragment, 21.2 24.4, 34.2 36.1 m (H2C, cyclo-
hexylidene); 54.2 d (C1, 1JCP 77.6 Hz); 65.7 (C6); 69.0
13. Reichardt, C., Solvents and Solvent Effects in Organic
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3
(C4); 73.4 d (C3, JCP 3.4 Hz); 78.9 (C5); 79.8 d (C2,
2JCP 9.6 Hz); 108.3 [O2 C(CH2)5 O3]; 108.6
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008