Synthesis, crystal structure and hydrolysis of novel isomeric cage (P-C/P-O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

Article abstract of DOI:10.1039/c6ra17983e

The reaction of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane with hexafluoroacetone leads to the simultaneous formation of regioisomeric cage (P-C/P-O)-phosphoranes, the structures of which are unequivocally confirmed by XRD. The rearrangement of the P-C-isomer to P-O-isomer with high stereoselectivity (>96%) takes place in methylene chloride solution with the retention of the phosphorus coordination. It was found that the stepwise hydrolysis of the P-O-isomer initially gives 2-(2,3-dihydroxy-1,2-diphenyl-3-trifluoromethyl-4,4,4-trifluorobutyloxy)-4,4,5,5-tetramethyl-2-oxo-1,3,2-dioxaphospholane as the only stereoisomer whose structure is also confirmed by XRD. Further hydrolysis of this compound leads to the formation of 2,3-dihydroxy-3-trifluoromethyl-4,4,4-trifluoro-1,2-diphenylbutylphosphate and pinacol, which forms the solvate in the crystal. Hydrolysis of the P-C-isomer yields 2-hydroxy-4,4,5,5-tetramethyl-2-oxo-1,3,2-dioxaphospholane, benzoin and hexafluoroisopropanol.

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ARTICLE
Synthesis, Crystal Structure and Hydrolysis of Novel Isomeric Cage
(P–C/P–O)-Phosphoranes on the basis of 4,4,5,5-Tetramethyl-2-(2-
oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and
Hexafluoroacetone
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Nadezhda R. Khasiyatullina,a Vladimir F. Mironov, *a,b Dmitry B. Krivolapov,a Ekaterina V.
Mironova,a,b and Oleg I. Gnezdilovc
www.rsc.org/
The reaction of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane with hexafluoroacetone leads
to the simultaneous formation of regioisomeric cage (P–C/P–O)-phosphoranes which structures were unequivocally
confirmed by XRD. The rearrangement of P–C-isomer to P–O-isomer with a high stereoselectivity (> 96%) takes place in the
methylene chloride solution with the retention of the phosphorus coordination. It was found that stepwise hydrolysis of
P–O-isomer initially gives 2-(2,3-dihydroxy-1,2-diphenyl-3-trifluoromethyl-4,4,4-trifluorobutyloxy)-4,4,5,5-tetramethyl-2-
oxo-1,3,2-dioxaphospholane as the only stereoisomer whose structure was also confirmed by XRD. Further hydrolysis of
this compound leads to the formation of 2,3-dihydroxy-3-trifluoromethyl-4,4,4-trifluoro-1,2-diphenylbutylphosphate and
pinacol forming the solvate in the crystal. Hydrolysis of P–C-isomer yields 2-hydroxy-4,4,5,5-tetramethyl-2-oxo-1,3,2-
dioxaphospholane,
benzoin
and
hexafluoroisopropanol.
Scheme 1 shows a synthetic possibilities of this approach on
the example of the reactions of benzodioxaphosphole
Introduction
derivatives
1 with hexafluoroacetone. It is assumed that the
Pentacoordinated
phosphorus
compounds
are
key
reactions proceed through intermediate P+–C–O– bipolar ions
followed by transfer of the reactive center on the exocyclic
unsaturated substituent and lead to the formation of
corresponding cage phosphoranes 2-4 bearing P–C-bond.30-32
intermediates in the reactions of phosphoryl group transfer,
which are important in the processes of cell viability,1-7 in the
origin and development of life.8 Such phosphorus derivatives
are intermediates in the nucleophilic substitution reactions at
tetrahedral phosphorus atom,9-13 among which the most
important for organic synthesis the Wittig,14 Appel,15,16 and
Mitsunobu17-19 reactions are well described. Therefore, the
synthesis, structure and chemical transformations of
phosphoranes attract considerable attention.20-27 Among the
diverse methods of the phosphoranes’ synthesis several
general approaches based on the addition reactions of P(III)-
derivatives to unsaturated systems, various reactions of
tetracoordinated phosphorus and substitution reactions at
P(V) themselves28,29 should be noted.
O
O
Y
O
O
P
F3C
CF3
P
O
O
O
1
X
X = MeC, Y = O;
X = N, Y = CHPh
O
CF3
Y=X
F3C
2-4
O
O
O
O
O
O
O
O
O
P
P
O
F3C
P
N
O
F3C
F3C
O
O
O
F3C
F3C
Ph
CF3
2
3
4
In recent years, we have developed an approach to the
preparation of phosphoranes based on the cascade reactions
of P(III)-derivatives, containing an unsaturated moiety, with
carbonyl compounds leading to P(V)–C cage heterocycles.30-34
Scheme
1 Use of P(III)-derivatives bearing an exocyclic C=O or C=N bond in the
synthesis of cage phosphoranes.
Scheme
2
demonstrates
a
synthetic potential of the
under
intramolecular cascade cyclization of P(III)-derivatives
1
the action of prochiral trifluoropyruvic acid ethyl ester and
chloral which allows obtaining the P–C-cage phosphoranes 5-8
with a high stereoselectivity.33,34
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13
,
14 are identical (ESI, m/z 523.9) and correspond to the
1; their
reaction products with composition of
1
:
fragmentation is not significantly different. After removal of
the solvent the oily residue crystallizes with the formation of
compound 13 during the storage. It manifests itself as a
3
doublet in the high-field region (CСl4, δP –25.1 ppm, JPCCH
=
15.6 Hz) of 31P-{1H} NMR spectrum. Taking into account the
spectral data (see ESI) we determined the structure of
compound
13
as
1-(2,3-butylenedioxy)-6,6-
Scheme 2 The reaction of P(III)-derivatives 1 bearing an exocyclic C=O bond with
bis(trifluoromethyl)-3,4-diphenyl-1,2,5,7-
phosphatrioxabicyclo[2.2.11,4]heptane. The 19F NMR spectrum
trifluoropyruvic acid ethyl ester and chloral.
4
3
contains two signals with δF –68.48 (qd, JFCCCF = 10.3 Hz, JPCCF
= 4.6 Hz) and
F –68.94 ppm (qd, 4JFCCCF = 10.3 Hz, 3JPCCF 2.3 Hz)
None of these reactions afford pentaalkoxyphosphoranes –
the products of intramolecular РСО/РОС-rearrangement which
is characteristic to the reaction of ordinary trialkylphosphites
with carbonyl compounds mentioned above.35,36
δ
with an equal integral intensity, which correspond to non-
equivalent fluorine atoms of СF3-groups. In contrast to the
above mentioned phosphite
9 – hexafluoroacetone system, in
Recently, we have shown37 that the inclusion of the
phosphorus(III) atom in dioxaphospholane cycle results in the
simultaneous formation of PCO- and POC-isomers (1 : 1) of
this case the formation of PC-phosphorane 13 is a kinetically
preferred process.
,11
cage phosphoranes10 in the reaction of 4,5-dimethyl-2-(2-
oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane9
with
hexafluoroacetone (Scheme 3). PCO-phosphorane 10 is
subjected to the intramolecular PCO/POC-rearrangement
during storage (CH2Cl2, 20°C, 30 days) and yields the POC-
species 11
.
Scheme 3 Simultaneous formation of PCO- and POC-isomers 10, 11 in the reaction of
phospholane 1 with hexafluoroacetone.
Results and discussion
Considering that the related РСО/РОС-rearrangement in a
series of 1-hydroxyalkylphosphonates (-phosphinates) is
facilitated not only electron-withdrawing substituents at the
carbon atom bonded with OH-group, but electron-donor ones
at the phosphorus atom38, we involved 4,4,5,5-tetramethyl-2-
(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane 12 to the
reaction with hexafluoroacetone. Tetramethyl-substituted
dioxaphospholane 12 has essentially more electron donor
cyclic moiety as compared with dimethyl-substituted
Scheme
4 The reaction of phospholane 12 with hexafluoroacetone. The same
numbering of the atoms in structures 13-17 is given for convenience of discussion.
The structure of phosphorane 13 was confirmed by the single
crystal XRD. The geometry of molecule 13 in crystal
(conglomerate) is shown in Fig. 1; main geometrical
parameters (bond lengths, bond and torsion angles) are listed
in the figure caption. Configuration of the chiral atoms is
P1 C3 C4 . A small deviation of the phosphorus atom from the
phospholane 9, which, however, also effectively stabilizes the
R
R
S
phosphorus pentacoordinated state. Compound 12 was
obtained by the phosphorylation of benzoin with 2-chloro-
4,4,5,5-tetramethyl-1,3,2-dioxaphospholane in the presence of
triethylamine according to the data.39
O3O2O6 plane [by –0.114(2)
Å] allows to conclude that the
phosphorus atom has a slightly distorted trigonal bipyramidal
configuration with a planar within 0.085(2)
Å base being
formed by the P1, O2, O3, C6 atoms. The O1 and O7 atoms
located in the apical positions, are deviated from this plane by
The reaction of phosphite 12 with hexafluoroacetone proceeds
in mild conditions (CCl4, –40
°
С) with simultaneous formation
14
P –24.5 and
–1.696 (5) 1.619(5)
(3
)]. One of the two trifluoromethyl groups (C25F3) is almost in
Å
[bond angle О1–Р1–О7 is equal to 172.4
of two isomeric pentacoordinated phosphorus species 13
,
°
(Scheme 4) which have two high-field signals with
δP –26.5 ppm in the 10 : 1 ratio in 31P-{1H} NMR spectrum (a
δ
this plane [С25 atom deviation from it is 0.21(1) ]. The О1–Р1–
Å
O3, О1–Р1–O2, О1–Р1–C6, О2–Р1–O7, О7–Р1–C6, О3–Р1–О7 bond
day after the reaction). Molecular ions peaks for compounds
2 | J. Name., 2012, 00, 1-3
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angles are varied within the limits of 83.3(3)-96.9(3)
Р1–С6, О2–Р1–O3, О3–Р1–C6 bond angles sum in the pyramid
base is equal to 358.5(2) and points to the trigonal
°
. The О2–
°
bipyramidal phosphorus configuration close to the almost
regular one. The Р1–О3 equatorial bond length is slightly
smaller [1.583(5)
[1.613(3) and 1.711(5)
A practice coincidence of the Р1–О1 and Р1–О7 axial bond
lengths sum [3.324(5) ] can
] and О1⋅⋅⋅О7 distance [3.317(7)
Å
] than the Р1–О1 and Р1–О7 axial ones
Å
].
Å
Å
be considered as the evidence of the regular trigonal
bipyramidal phosphorus configuration. The Р1–С6 bond length
is equal to 1.930(7) Å. Five-membered dioxaphospholane cycle
occupies axial-equatorial position in trigonal bipyramid (О1 is
axial, О3 is equatorial), its conformation is envelope, where
four atoms О1, Р1, О3, С8 are lying in one plane [planar within
0.004(5)
С9 and С12 atoms are deviated from this plane on 2.05(1) and –
1.43(1) correspondingly, they occupy axial positions in the
cycle. С10 and С11 atoms are also deviated from the О1Р1О3С8
Å Å.
], С7 atom is deviated from this plane on 0.518(9)
Fig. 1 Geometry of molecule 13 in crystal (conglomerate). Selected bond lengths (Å),
bond and torsion angles (°): P1–O1 1.613(5), P1–O2 1.619(5), P1–O3 1.583(5), P1–O7
1.711(5), P1–C6 1.930(7), O1–P1–O2 96.3(3), O1–P1–O3 92.7(3), O1–P1–O7 172.4(3), O1–
P1–C6 92.8(3), O2–P1–O3 120.9(3), O2–P1–O7 90.3(2), O2–P1–C6 100.7(3), O3–P1–O7
85.7(2), O3–P1–C6 136.9(3), O7–P1–C6 83.3(3), C9–C7–C8–C12 –161.4(8), P1–O7–C4–C19
177.5(5), C13–C3–C4–C19 46.2(8), O7–C4–C19–C20 1(1). Hereinafter non-hydrogen atoms
are shown in view of thermal ellipsoids with a probability of 30%; the trigonal pyramid
base is outlined with thin lines.
Å
plane on –0.05(1) и 0.91(1)
Å and located in equatorial
positions. О2 and С6 atoms are deviated in the opposite sides
from the О1Р1О3С7 plane [their deviations are 1.377(5) and –
1.297(8)
membered cycle. C10 and O7 deviations are minimal [they are
deviated on –0.05(1) and –0.213(5) ] and we can assume that
they are lying in the О1Р1О3С8 plane.
Å] and occupy equatorial and axial positions in five-
Å
During storage in more polar dichloromethane at 20°С for
about five days the compound 13 underwent a gradual
The О1Р1О3С8 fragment can also be considered as a part of the
conversion to the compound 14 (after four days the ratio of
most elongated seven-membered approximately planar
С8О3Р1О1O7C4C19 system [planar within 0.135(5)
Å
]. The plane
of phenyl substituent in fourth position of the bicycloheptane
13 is slightly turned on the dihedral angle of 6.2(5) relative to
compounds 13/14 was 1 to 20). Fig. 2 shows the spectral
picture of this process according to the 31P-{1H} NMR. The
figure shows that the phosphorane 13 (CH2Cl2, δP –25.0 ppm)
completely converted to pentaoxyphosphorane 14 (CH2Cl2, δP
–26.7 ppm), which was a minor compound in the reaction in
tetrachloromethane. This compound was isolated in individual
state by the crystallization under a layer of pentane and
characterized by spectral methods, which allowed to assign
the structure of 1-(2,3-butylenedioxy)-5,5-bis(trifluoromethyl)-
3,4-diphenyl-1,2,6,7-phosphatrioxabicyclo[2.2.11,4]heptane 14
– the product of PCO/POC-rearrangement. In the 13C-{1H} NMR
spectrum of the compound 14 the carbon atom bonded to CF3-
groups, resonates at 83.41 ppm as a septet with coupling
constant through two bonds from fluorine (2JCCF = 29.3 Hz),
unlike the spectrum of the compound 13 in which the
oxygenated carbon in OС(СF3)2 fragment manifests itself as a
doublet of septets at 77.78 ppm with direct spin-spin coupling
constant from phosphorus (1JPС = 154.8 Hz, 2JFСС = 30.7 Hz). The
signals of CF3-groups in 19F NMR spectra of compound 14
appear as two quartets with δF –68.22 ppm and –72.35 ppm
°
the seven-membered fragment. The conformation of five-
membered P1O2С3C4O7 cycle of molecule 13 is envelope (Fig.
1). It includes four-membered plane P1O2С3C4 fragment [planar
within 0.025(5)
0.760(5)
. О1, О3, О5, С6, С13, С19 atoms are deviated from the
above fragment on the values of –0.742(5), 1.302(5), –
1.391(5), –1.574(7), 1.257(7) и 0.355(3) respectively. The
Å
], O7 atom is deviated from this plane on
Å
Å
fact that С13 and С19 atoms are deviated to one side points out
on cis-orientation of phenyl substituents in discussed five-
membered cycle. The conformation of the other five-
membered P1C6O5C4O7 ring of the rigid bicycloheptane scaffold
is a slightly distorted envelope. The four-membered P1C6O5C4
fragment is planar within 0.066(5)
this plane on –0.853(5)
. О1, О2, О3, С3, С19, С25, C26 atoms are
deviated from the above fragment on the values of –0.699(5),
Å
, O7 atom is deviated from
Å
1.392(5), –0.949(5), 1.337(7), –0.579(7), –1.40(1) и 1.097(9)
correspondingly.
Å
(
4JFCCCF = 9.5 Hz).
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where four О1, Р1, О3, С7 atoms are lying in one plane [planar
within 0.0482(7)
], and С8 atom is deviated from the above
plane on 0.422(4)
. С9 and С12 atoms are deviated from the
plane to the opposite sides on rather significant distances of –
1.525(5) and 1.963(6) correspondingly (they occupy axial
positions in cycle), С10 and С11 atoms are also deviated on
different values of 0.758(5) and –0.178(6) (they occupy
Å
Å
Å
Å
equatorial positions in cycle). О2 and O6 atoms are deviated to
the opposite sides from О1Р1О3С7 plane and occupy equatorial
and axial positions in five-membered cycle [their deviations
are 1.182(2) and –1.406(2)
Å
respectively]. The О7 atom
], thus it can be concluded
deviation is minimal [–0.213(5)
Å
that thus atom is lying in the О1Р1О3С7 plane. Also it should be
noticed that О1Р1О3С7 fragment is turned to be a part of more
extended planar moiety of С7О3Р1О1О3O7C4C19 in molecule
[planar within 0.054(4) Å]. The plane of phenyl substituent in 4
position (C19-24) is slightly turned regarding to this seven-
membered fragment [the dihedral angle between the
corresponding planes is larger than the one in molecule 13 and
is equal to 9.2(2)
P1O2С3C4O7 cycle of the rigid bicycloheptane system of
molecule 14 is envelope [it contains planar within 0.033(2)
four-membered P1O2С3C4 fragment, and O7 atom is deviated
from it on 0.806(2)
]. О1, О3, С5, O6, С13 and С19 atoms are
°]. The conformation of five-membered
Å
Å
deviated from the above planar fragment on the values of –
0.726(2), 1.224(2), –1.428(3), –1.341(2), 1.276(3) and 0.485(3)
correspondingly. The fact, that С13 and С19 atoms are
Å
Fig 2 A conversion of P–C-phosphorane 13 to P–O-species 14 according to 31P-{1H} NMR
deviated to one side, points out to the cis-orientation of
phenyl substituents in the above five-membered cycle. The
conformation of the other five-membered P1O6C5C4O7 cycle of
the rigid bicycloheptane system of molecule 14 is slightly
distorted envelope [four-membered P1O6C5C4 fragment is
spectra (CH2Cl2, in a day, after two, three and five days).
Its structure was also confirmed by a single crystal XRD. In the
Fig. 3 the geometry of the molecule in crystal is presented (the
main geometrical parameters including bond length, valence
and torsion angles of the molecule above are presented in
Supporting Information file).The configuration of chiral atoms
is P1 C3 C4 / P1 C3 C4 (racemate). A meaningless deviation of
planar within 0.044(3)
fragment on –0.851(2)
Å
Å
, O7 atom is deviated from the above
]. О1, О2, О3, С3, С19, С25 and C26 atoms
are deviated from the above planar fragment on the values of
0.804(2), 1.364(2), –1.078(2), 1.322(3), –0.576(3), 1.366(4) and
R
R
S
S
S
R
phosphorus atom from О3О2С6 plane on –0.0580(7)
Å allows to
conclude, that the geometry of phosphorus in molecule 14 is
–1.151(4)
Å correspondingly.
slightly distorted trigonal bipyramid with the planar base
[within 0.043(2)
and О7 atoms located in apical positions are deviated from the
above plane on the values of –1.625(2) and 1.700(2) [the
]. The values of
Å
], where Р1, О2, О3, С6 atoms are located. О1
Å
valence angle О1–Р1–О7 is equal to 177.5(1)
°
the valence angles О1–Р1–O3, О1–Р1–O2, О1–Р1–O6, О2–Р1–O7,
О6–Р1–O7, О3–Р1–О7 are varied within the limits of 86.1(1)-
92.4(1)
Р1–O6 at the pyramid base is 359.6(2)
°
, the sum of valence angles О2–Р1–O6, О2–Р1–O3, О3–
°
, that also points out the
trigonal-bipyramidal configuration of phosphorus atom close
to the regular one. The equatorial Р1–О2, Р1–О3, Р1–О6 bonds
[1.606(2), 1.582(2), P1–O6 1.647(2),
Å
] are slightly shorter than
the axial ones Р1–О1 and Р1–О7 [1.625(2) и 1.700(2)
Å
]. In favor
of regular trigonal bipyramid configuration is the fact of
practical coincidence of Р1–О1 and Р1–О7 axial bond values sum
[3.325(5)
Å Å]. The five-
] and О1⋅⋅⋅О7 distance [3.323(7)
membered tetramethyldioxaphospholane cycle occupies axial-
equatorial position in trigonal bipyramid (О1 atom is axial, О3
Fig 3 Geometry of molecule 14 in crystal (racemate, Р1SС3SС4R-enantiomer is shown).
The base of trigonal bipyramid shown by thin lines. Selected bond lengths (Å), bond
atom is equatorial). Its conformation is the distorted envelope
,
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and torsion angles (°): P1–O1 1.625(2), P1–O2 1.606(2), P1–O3 1.582(2), P1–O6 1.647(2),
P1–O7 1.700(2), O1–P1–O2 92.1(1), O1–P1–O3 92.4(1), O1–P1–O7 177.5(1), O1–P1–O6
91.6(1), O2–P1–O3 126.4(1), O2–P1–O7 90.4(1), O2–P1–O6 105.8(1), O3–P1–O7 86.1(1), O3–
from O1P1O3C8 plane on 1.574(5), –1.990(8) and 1.552(8) Å
respectively). O4, C10 and C11 atoms are located in equatorial
positions and deviated from the O1P1O3C8 plane on –0.851(4),
P1–O6 127.4(1), O6–P1–O7 87.8(1), C9–C7–C8–C11 –164.4(4), P1–O7–C4–C19 178.8(2), C13
C3–C4–C19 –40.9(3), O7–C4–C19–C20 10.0(4).
–
0.20(1) and –0.713(9) Å. Due to the presence of solvent water
molecule in crystal of 15 classical hydrogen bonds’ system is
realized with the participation of phosphoryl O4 oxygen and
water molecule protons [O1S–H1S⋅⋅⋅O4-interaction, the
Considering that compound 13 and 14 are formed
simultaneously in the very mild conditions (–40 С), and
°
rearrangement of P–C-isomer 13 into the P–O-isomer 14 is
parameters are: O1S–H1S 0.72(9)
Å
, H1S⋅⋅⋅O4 2.0(1)
, symmetry operation –1/2 +
]; and also between hydrogen at O2 atom and
water oxygen O1S [O2–H2⋅⋅⋅O1S-interaction, the parameters are:
O2–H2 0.86(7) , H2⋅⋅⋅O1S 1.61(7) , O2⋅⋅⋅O1S 2.46(1) O2–
2⋅⋅⋅O1S 168(9)
, symmetry operation 1 + x, y, z]. Using those
classical hydrogen interactions the molecules of 15 in crystal
form ribbons along the 0 crystallographic axis (see Fig. 5).
Å
, O1S⋅⋅⋅O4
2.75(1)
x, 1/2 – y, 1 –
Å, ∠ °
O1S–H1S⋅⋅⋅O4 178(8)
slow, it can be assumed that they are formed from a common
containing
z
unstable
phosphorane
intermediate
A
,
oxaphosphirane cycle (Scheme 4). This intermediate is a
product of the symmetry allowed [1+2]-cycloaddition reaction
of phosphorus to the double bond of hexafluoroacetone.
Already at low temperature a cleavage of three-membered
Å
Å
Å, ∠
H
°
a
ring occurs in two directions
formation of compounds 13 and 14. The direction
P–O bond cleavage and the formation of intermediate bipolar
ions and is kinetically controlled and reversible process.
Direction II – P–C bond cleavage and the formation of
intermediate bipolar ions and – irreversibly results in
I
and II, finally resulting in the
I, including a
B
C
D
E
thermodynamically controlled reaction product – P–O-isomer
14. Thus, the driving force of the PCO/POC-rearrangements
seems to be a greater thermodynamic stability of the resulting
pentaalkoxyphosphorane 14 in comparison with its P–C-
analogue 13. Furthermore oxygen is more electronegative
than carbon, and it is important for the stabilization of the
phosphorus trigonal bipyramid, which increases its stability
when the acceptors are introduced to the phosphorus atom.
Since in the synthesis of phospholane 12 racemic benzoin was
used, and in the reaction with hexafluoroacetone another
chiral carbon (C4) formation occurred, two P–C
diastereoisomers of isomer 13 should be formed. The
formation of only one diastereoisomer indicates a high
stereoselectivity of the second chiral center (C4) formation,
which is probably due to the rigid spatial requirements for the
attack of alkoxide-anion to the carbonyl group of the bipolar
Fig 4 Geometry of molecule 15 in crystal (solvate with water). Selected bond lengths
(Å), bond and torsion angles (°): P1–O1 1.568(6), P1–O2 1.533(7), P1–O3 1.572(6), P1–O4
1.477(6), O1–P1–O3 98.6(2), O1–P1–O2 108.5(3), O2–P1–O4 113.5(3), O1–C7–C8–O3
36.9(6), C9–C7–C8–C11 33.6(8), C10–C7–C8–C12 34.5(8).
ion
chiral C3 and C4 atoms in the P–C- and P–O-isomers 13
according to XRD data, is the same, indicating
B
. It is very important fact that the relative configuration of
14
high
,
,
a
stereoselective nature of intramolecular PCO/POC-
rearrangement.
Hydrolysis of P–C-isomer 13 leads to the formation of
dioxaphospholane 15, benzoin, and hexafluoroisopropanol.
Benzoin and compound 15 were isolated by crystallization of
the reaction mixture from diethyl ester. Benzoin and
hexafluoroisopropanol structure was proved by comparison of
their spectral characteristics (1H, 13C, 19F NMR) with known in
the literature.40-43 Structure of dioxaphospholane 15 was
established based on the comparison of the spectral
parameters with those described in the literature44,45 and the
XRD.
Fig 5 System of the intermolecular hydrogen bonds in a crystal of compound 15.
Mild stepwise hydrolysis of P–O-isomer 14 leads to the initial
formation of dioxaphospholane 16. The 31P NMR spectrum of
The geometry of the molecule in crystal (solvate with one
water molecule) is presented in the Fig. 4. The Five-membered
cycle of molecule 15 has an envelope conformation with
3
this compound contains the doublet (δР 11.0 ppm, JPССH 5.9
Hz) with a coupling constant from the proton at C3, indicating
the retention of P–O–C3 fragment. The 13C NMR spectrum
shows the spin-spin coupling of all the methyl carbons with
accordingly planar within 0.115(4) Å
atom is deviated from the above plane on –0.492(8)
O1P1O3C8 fragment, С7
. O2, C9
Å
and C12 atoms are located in axial positions (they are deviated
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Journal Name
phosphorus atom, that clearly points to the retention of
4,4,5,5-tetramethyl-1,3,2-dioxaphospholane cycle. This data
are in accordance with breaking of the P1–O2 and P1–O7 bonds
in phosphorane 14 during the hydrolysis. The result of
hydrolysis of phosphorane 14 differs from one for compound
11 containing 4,5-dimethyl-1,3,2-dioxaphospholane moiety. In
the last case the 2,3-butanediol elimination proceeds.37
The structure of phospholane 16 was confirmed using single
crystal XRD. In the Fig. 6 the geometry of the molecule in
crystal is presented (the main geometrical parameters
including bond length, valence and torsion angles of the
molecule 16 are presented in the ESI). The phosphorus atom
has a distorted tetrahedral configuration. Dioxaphospholane
cycle has an envelope conformation with planar within
0.080(6)
deviated from this plane on 0.510(9)
C12 atoms are in axial positions (they are deviated from
Å
four-membered O1P1O3C7 fragment, and С8 atom is
(see Fig. 7). O2, C10 and
Fig 6 Geometry of molecule 16 in crystal (racemate, С3RС4S-enantiomer is shown).
Selected bond lengths (Å), bond and torsion angles (°): P1–O1 1.582(6), P1–O2 1.581(6),
P1–O3 1.583(7), P1–O4 1.460(6), O2–C3 1.478(9), O1–P1–O2 101.2(3), O1–P1–O3 99.6(3),
Å
O1P1O3C8 plane on the values of 1.260(5), –1.52(1) and 2.05(1) O1–P1–O4 118.9(4), O2–P1–O3 109.6(3), O2–P1–O4 112.7(3), O3–P1–O4 113.4(4), P1–O2–
C3–C4 163.2(5), O7–C4–C5–O6 165.2(6), O2–C3–C4–O7 46.1(8).
Å
correspondingly). O4, C9 and C11 atoms are in equatorial
positions (they are deviated from O1P1O3C8 plane on the values
of –1.265(6), 0.74(1) and –0.05(1) correspondingly). The
Å
presence of four methyl groups leads to a noticeable deviation
of conformation along the C7–C8 bond from the regular
staggered gauche one due to the steric repulsion (the torsion
angles C9C7C8C12 and C10C7C8C11 are equal to –39(1) and –
36(1)°). The envelope conformation is probably realized in
solution of the investigated compound too, that is confirmed
by non-equivalence of these four methyl groups in NMR 1H
and 13C spectra, and also by different spin-spin coupling
Fig 7 Conformation of 1,3,2-dioxaphospholane cycle along C7–C8 bond in 16 (acyclic
3
substituent is omitted for clarity).
constants JPCCC, which depend on the P–C–C–C torsion angle
values. The same situation is realized for the conformation
along C3–C4 bond (the torsion angles O2C3C4O7 and С13C3C4С16
are 46.2(9) and –45.2(9)°). The repulsion between two phenyl
groups probably has the less meaning in comparison with the
phenyl and hexafluoroisopropylhydroxy-substituent repulsion,
that leads to the such conformation along C3–C4 bond (the
torsion angle С5C4C3С13 is –166.7(7)
°). Due to the classical
hydrogen bond O6–H6⋅⋅⋅O4 the molecules of 16 are connected
in dimers, and thus, the 0D supramolecular structure is
realized in crystal [the parameters of the interaction are: O6–
H6 0.66(6)
Å
, H6⋅⋅⋅O4 2.14(6)
Å
155(7) , symmetry operation 1 –
, O6⋅⋅⋅O4 2.76(1) Å,
∠
O6–H6 ⋅⋅⋅O4
, 2 – , – ]. The packing of
°
x
y
z
the molecules 16 in crystal is also stabilized by the
intramolecular bifurcate O(7)–H7⋅⋅⋅F1 and O7–H7⋅⋅⋅O(2) classical
hydrogen bond [the parameters are: O7–H7 0.87(8)
Å
, H7⋅⋅⋅F1
; and H7⋅⋅⋅O2
O7–H7⋅⋅⋅O2 118(6)
2.34(9)
2.20(7)
Å
, O7⋅⋅⋅F1 2.860(9)
Å, ∠ °
O7–H7⋅⋅⋅F1 119(8)
Å,
O
7⋅⋅⋅O2 2.722(8)
Å
,
∠
°
respectively, see Fig. 8].
Fig 8 The system of classical hydrogen bonds in crystal of 16.
Prolonged hydrolysis of phosphorane 14 leads to the cleavage
not only of the exocyclic P1–O6 and P1–O7 bonds but the 1,3,2-
dioxaphospholane P–O bonds as well. The process is
accompanied by the formation of 2,3-dihydroxy-3-
trifluoromethyl-4,4,4-trifluoro-1,2-diphenylbutylphosphate 17
and pinacol. It should be noted, that phosphate 17 (δР –1.4
6 | J. Name., 2012, 00, 1-3
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ppm,
δF –67.05 and –67.82 ppm (CDCl3/DMSO-d6, 3 : 1)) exists
in equilibrium with a cyclic form 19
(
δР 14.7 ppm (CD3CN), δF
–
68.42 and –69.98 ppm (CDCl3/DMSO-d6, 3 : 1)) (Scheme 5) in
solution.37 A ratio of cyclic and acyclic phosphates in reaction
medium is close to 1:10, however this equilibrium shifts to the
formation of a cyclic derivative 19 upon heating (40ºС) and the
ratio became 2 : 1. Long crystallization of hydrolysis products
from CH2Cl2 allowed isolating the crystalline complex 18 of this
acyclic monophosphate 17 with pinacol in 2 : 1 ratio. The
structure of complex 18 was confirmed by XRD. The geometry
of the complex in a crystal and atom numbering are shown in
Fig. 9; main geometrical parameters (bond lengths, bond and
torsion angles) are listed in the figure caption. Phosphorus
atom has a distorted tetrahedral configuration; configuration
of the chiral atoms is С3 С4 / С3 С4 . The conformations of the
S
R
R
S
monophosphate 17 and pinacol molecules along C4–C3, C5–C4
Fig 10 A view of conformations for the molecule (17) in front of the C4–C3 (a), C5–C4 (b)
and C6–C6a bonds are shown in Fig. 10. All of them are closely and C6–C6a (c) bonds.
related to the almost regular staggered species. Phenyl
substituents are located in gauche-conformation along C4–C3
Due to the classical O–H⋅⋅⋅O hydrogen bonds of the molecules
of 17 and pinacol form sheets along the b0c crystallographic
plane, and thus, the 2D supramolecular structure is realized in
crystal [the parameters of the interactions are: O1–H1⋅⋅⋅O(4)
bond [the torsion angle C13–C3–C4–C19 is –50.1(6)
°].
Trifluoromethyl groups have different orientations relative to
the phenyl ring at the C4 atom (see Fig. 10) and therefore the
fluorine atoms exhibit non-equivalence in the 19F NMR
spectrum owing to the phenyl ring anisotropy.
interaction: O1–H1 0.86(6)
O1–H1–O4 152(9)
O3–H3⋅⋅⋅O5 interaction: O3–H3 0.98(7)
3⋅⋅⋅O5 2.639(6) O3–H3–O5 165(5)
1 + , 1 + , –1 +
; O7–H7⋅⋅⋅O4 interaction: O7–H7 0.99(9)
7⋅⋅⋅O4 1.85(7) , O7⋅⋅⋅O4 2.802(6) O7–H7–O4 159(8)
symmetry operation , 3/2 – , 1/2 +
Å
, H1⋅⋅⋅O4 1.76(6)
, symmetry operation
, H3⋅⋅⋅O5 1.68(7)
, symmetry operation –
Å
x
, O1⋅⋅⋅O4 2.547(6)
Å
,
∠
°
, 3/2 – , 1/2 +
y
z;
Å
Å,
Ph
O
Å
,
∠
z
°
3
CF3
O
- H2O
H2O
x
y
Å,
4
CF3
OH
17
HO
P
5
H
Å
Å,
∠
z
°,
O
O
Ph
x
y
]. The packing of the
19
molecules 17 in crystal of solvate 18 is also stabilized by the
intramolecular O7–H7⋅⋅⋅F1 classical hydrogen bond [the
Scheme 5 The equilibrium of phosphates 17 and 19 in dioxane solution.
parameters are: O7–H7 0.99(9)
Å Å
, H7⋅⋅⋅F1 2.31(9) , O7⋅⋅⋅F1
2.757(6) Å, ∠ °, see ESI].
O7–H7–F1 106(7)
Experimental
1-(2,3-Butylenedioxy)-6,6-bis(trifluoromethyl)-3,4-diphenyl-
1,2,5,7-phosphatrioxabicyclo[2.2.11,4]heptane
13
.
Hexafluoroacetone (4.81 g, 30 mmol) was condensed into
ССl4/CH2Cl2 (1 : 1) solution (40 mL) of dioxaphosphole 12 (10.4
g, 30 mmol) at –40°С. Reaction mixture was warmed up to
20 С (10 h) and then evaporated under reduced pressure (14
°
Torr) to give a white precipitate of 13, which was filtered off
Fig 9 Geometry of complex 18 in crystal (solvate of molecule 17 with 1/2 pinacol,
racemate, С3SС4R-enantiomer is shown). Selected bond lengths (Å), bond and torsion
angles (°): P1–O1 1.535(5), P1–O2 1.588(4), P1–O3 1.551(4), P1–O4 1.489(4), O1–P1–O2
103.4(2), O1–P1–O3 102.6(3), O1–P1–O4 116.9(3), O2–P1–O3 109.1(2), O2–P1–O4 111.3(2),
O2–C3–C4–C5 58.8(6), P1–O2–C3–C4 –168.4(3), C3–C4–C5–C26 –163.4(5).
and dried in vacuo (14 Torr). Yield 7.12 g (47 %), mp 122-
125°С. The filtrate was evaporated in vacuo (14 Torr) under
argon atmosphere to give a pale yellow oil, which gradually
crystallized under a pentane layer (–18°C). Clear white crystals
of compound 13 were filtered off. Yield 3.62 g (24 %), mp 123-
125°С. Anal. Calcd. for C23H23F6O5P (524.12): С, 52.68; Н, 4.42;
Р, 5.91. Found: С, 52.63; Н, 4.39; Р, 5.98. IR (KBr) (νmax, cm–1):
2987, 2947, 1454, 1398, 1378, 1342, 1277, 1262, 1231, 1199,
1155, 1141, 1080, 1048, 1006, 979, 936, 883, 84, 816, 793,
770, 748, 719, 694, 666, 635, 539, 476. 1Н NMR (400 MHz,
СDCl3) / δ (ppm): 7.30 (m, 2H), 7.18 (m, 5H), 7.10 (m, 3H), 5.46
(d, 1H, 3JРOСН = 17.0 Hz, Н3), 1.49 (br. s, 12H, CН3). 13C / 13С-{1H}
NMR (100.6 МHz, СDCl3), (hereinafter a view of signal in 13C-
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1
3
{1H} NMR spectrum is in parentheses) / δC (ppm): 135.74 (m 3JHCCC = 4.4 Hz, C9-C7eq), 23.69 (qdq (d), JHC = 127.6 Hz, JPOCC
=
(d), 3JНCCС = 7.7 Hz, 2JHCС = 5.2 Hz, 3JРOCС = 0.7 Hz, С13), 133.36 (dt 5.2 Hz, 3JHCCC = 4.4 Hz, C10-C7eq), 23.54 (qdq (d), 1JHC = 127.5 Hz,
(d), JРOСС = 12.2 Hz, JНССС = 7.5 Hz, С19), 129.18 (dt (s), JНС
=
3JPOCC = 7.7 Hz, JHCCC = 4.4 Hz, C11-C8ax), 23.36 (qdq (d), JHC
=
3
3
1
3
1
160.7 Hz, JHССС = 7.4 Hz, С22), 128.61 (dm (s), JНС = 161.0 Hz, 127.5 Hz, JPOCC = 8.0 Hz, JHCCC = 4.4 Hz, C12-C8ax). 19F NMR
3
1
3
3
1
3
4
3JHССС = 7.2 Hz, С16), 128.09 (br. dd (s), JНС = 160.3 Hz, JHCCС
=
(376.5 MHz, CDCl3) / δF (ppm): –68.22 (q, JFCCCF = 9.5 Hz), –
7.4 Hz, С15,17), 127.90 (dd (s), JНС = 161.0 Hz, JHCСС = 7.0 Hz, 72.35 (q, JFCCCF = 9.5 Hz). 31Р-{1H} / 31Р NMR (161.9 МHz,
1
3
4
С21,23), 127.21 (br. ddd (s), JНС = 159.6 Hz, JНССС = 6.2-6.3 Hz, CDCl3) / δР (ppm): –27.3 (d (s), JPOСH = 20.4 Hz). ESI–MS (m/z):
1
3
3
3JHCCС = 6.2-6.3 Hz, С14,18), 125.82 (ddd (s), 1JHС = 161.1 Hz, 3JНССС 523.97.
= 7.4 Hz, 3JHCCС = 6.2 Hz, С20,24), 122.60 (qd (qd), 1JFС = 285.8 Hz,
1
2
2JРCС = 1.1 Hz, С26), 121.71 (br. qd (qd), JFС = 289.8 Hz, JРCС
=
Hydrolysis of compound 13. To the suspension of compound
5.7 Hz, С25), 99.76 (ddm (d), JРOС = 23.9 Hz, JHCС = 4.2-4.4 Hz, 13 (1 g, 1.91 mmol) in diethyl ester (5 mL) a solution of 0.1 mL
2
2
1
2
3JHCCС = 4.2-4.4 Hz, С4), 87.68 (dmd (d), JНС = 156.3 Hz, JРOС
=
=
(5.72 mmol) of water in 3 mL of diethyl ester was added
dropwise with constant stirring. The resulting white crystalline
2.9 Hz, JHCCС = 4.4 Hz, C3), 82.93 (m (d), JРOС = 2.2 Hz, JHCС
3
2
2
4.2-4.4 Hz, С8eq), 79.17 (m (d), JРOС = 2.9 Hz, JHCС = 4.4 Hz, precipitate of compound 15 (hydrate with one H2O molecule)
2
2
С7ax), 77.78 (d. sept (d. sept), JPС = 154.8 Hz, JFСС = 30.7 Hz, was filtered off and dried in vacuo (14 Torr). Yield 0.31 g (83
1
2
С6), 23.52 (br. qdq (br. d), JHС = 127.3 Hz, JPOСС = 11.0 Hz, %), mp 190-192
3JНССС = 4.0 Hz, С9-12). 19F NMR (376.5 MHz, СDCl3) / F (ppm): – 1H, OH), 1.41 (br. s, 12H, Н9-12). 31Р-{1H}NMR (161.9 МHz,
68.44 (q. d, 4JFCCCF = 10.3 Hz, 3JPCCF = 4.6 Hz), –68.87 (q, 4JFCCCF Р: 10.6 ppm (s). The 1H NMR spectral data of the
DMF-d7),
10.3 Hz, 3JPCCF = 2.3 Hz). 31Р-{1H} / 31Р NMR (161.9 МHz, CDCl3) aliquot of the filtrate contain the benzoin and
°C. Н NMR (400 MHz, DMF-d7), δ: 8.72 (br. s,
1
3
1
δ
=
δ
3
3
/ δР (ppm): –25.1 (dd (s), JPССH = 17.6 Hz, JPССF = 1.9 Hz). ESI– hexafluoroisopropanol
signals.
Hexafluoroisopropanol
MS (m/z): 523.97.
structure was proved by comparison of their spectral
characteristics (1H, 13C, 19F NMR) with previously published.43
The filtrate was evaporated in vacuo (14 Torr) to give a white
1-(2,3-Butylenedioxy)-5,5-bis(trifluoromethyl)-3,4-diphenyl-
1,2,6,7-phosphatrioxabicyclo[2.2.11,4]heptane 14. The mixture precipitate of benzoin, mp 132-134
°
C. 1H NMR (600.0 МHz,
(ppm): 8.03 (m, 2H, XX’-part of
3JA’X’ = 7.5 Hz, H20,24), 7.56 (tt, 1H, 3JAM
4JX’M’ = 1.5 Hz,
-part of AA’MXX’
of compound 13 (6.00 g, 11.45 mmol) and CH2Cl2 (20 mL) was acetone-d6 / СDCl3 = 2 : 1) /
kept for five days (control by 31P NMR). After completing of the AA’XX’-subsystem, 3JAX
δ
=
=
4
rearrangement the reaction mixture was evaporated in vacuo
=
3JA’M = 7.5 Hz, JXM
M
-
(14 Torr) under argon atmosphere to give a yellow oily residue, system, H22), 7.45 (br. dd, 2H, AA’-part of AA’XX’-subsystem,
which was gradually crystallized during the storage under a 3JAX
=
3JA’X’ = 7.5 Hz, JAM
=
3JA’M’ = 7.5 Hz, H21,23), 7.44 (m, 2H,
3
3
pentane layer (–18°C). The crystalline precipitate of 14 was XX’-part of AMM’XX’-system, JXM
=
3JX’M’ = 7.5 Hz, H14,18), 7.32
filtered off and dried in vacuo (14 Torr). Yield 5.34 g (89 %), mp (br dd, 2H, MM’-part of AMM’XX’-system, 3JXM
125-127 -part of AMM’XX’
С. Anal. Calcd. for C23H23F6O5P (524.12): С, 52.68; Н, 3JAM 3JAM’ = 7.5 Hz, H15,17), 7.25 (tt, 1H,
4JAX’ = 1.5 Hz, H16), 6.13 (s,
=
3JX’M’ = 7.5 Hz,
°
=
A
-
3
4
4.42; Р, 5.91. Found: С, 52.64; Н, 4.40; Р, 5.93. IR (KBr) (νmax
,
system, JAM = =
3JAM’ = 7.5 Hz, JAX
cm–1): 3067, 3036, 2984, 2938, 1500, 1460, 1452, 1396, 1378, 1H, H3), 4.93 (br. s, 1H, OH). 13C / 13С-{1H} NMR (150.0 МHz,
2
3
4
1288, 1241, 1164, 1103, 1042, 1014, 982, 949, 899, 879, 853, acetone-d6 / СDCl3 = 2 : 1) / δC (ppm): 200.01 (br. dt (s), JHC
C
3
833, 805, 783, 754, 738, 714, 713, 695, 666, 604, 581, 560, = 3.5 Hz, JHC
4
= 3.3 Hz, C ), 140.75 (tdd (s), JHC
3
20,24
4
15,17 13
=
CC
CC
1
3
13
= 5.5 Hz, JHOCC = 1.3 Hz, C ), 135.36 (br. t (s),
(ppm): 7.44 (m, 7.5 Hz, 2JHC
3
13
13
498, 486, 461. Н NMR (400 MHz, СDCl3) /
δ
C
1H), 7.30 (m, 1H), 7.17 (m, 3H), 7.08 (m, 5H), 5.72 (d, 1H, 3JРOСН
= 19.2 Hz, Н3), 1.52 (s, 3H, CH3), 1.51 (s, 3H, CH3), 1.43 (s, 3H,
CH3), 1.38 (s, 3H, CH3). 13C / 13С-{1H} NMR (100.6 МHz, СDCl3) /
JHC
JHC
JHC
= 7.4 Hz, C19), 134.27 (dt (s), JHC = 162.9 Hz,
3
1
21,23 19
22
CC
22 = 7.7 Hz, C22), 129.86 (ddddd (s), 1JHC20,24 = 161.3 Hz,
3
3
20,24
CC
3
= 7.6 Hz, JHC
2
= 7.6 Hz, JHC
24,20 20,24
CC
22 20,24
21,23 20,24
C
= 1.7
15,17
CC
δC (ppm): 135.40 (tt (s), JHCCC = 5.1-5.3 Hz, JHCC = 2.2 Hz, C13), Hz, JHC
= 1.3 Hz, C20,24), 129.52 (br. dm (s), JHC
=
3
2
4
1
4
20,24
CCC
131.08 (dt (d), 3JPOCC = 18.7 Hz, JHCCC = 7.2 Hz, C19), 128.59 (dm 161.5-161.8 Hz, JHC
= 6.0-7.0 Hz, C15,17), 129.41 (dd
3
3
15,17 17,15
CC
1
3
3
1
3
= 161.7 Hz, JHC
(s), JHC = 160.7 Hz, JHCCC = 7.3 Hz, JHCCC = 7.3 Hz, C16 or C22), (s), JHC
= 7.6 Hz, C21,23), 128.84
21,23
23,21 21,23
CC
1
3
3
1
3
128.56 (dm (s), JHC = 160.7 Hz, JHCCC = 7.3 Hz, JHCCC = 7.3 Hz, (dtd (s), JHC = 161.0 Hz, JHC
5
= 7.6 Hz, JHC
16
14,18 16
3
16
= 1.1
14,18 = 6.5-
CC
CCCC
C16 or C22), 128.52 (dm (s), 1JHC = 161.4 Hz, 3JHCCC = 7.3 Hz, 3JHCCC Hz, C16), 128.44 (dm (s), 1JHC14,18 = 162.4 Hz, JHC
3
18,14
CC
= 7.3 Hz, C14,18), 127.98 (br. dd (s), JHC = 160.5 Hz, JHCCC = 7.2 7.5 Hz, JHC
= 4.5 Hz, C14,18),
1
3
3
3
= 6.5-7.5 Hz, JHC
16 14,18
3
14,18
CC
CC
3
Hz, C23), 127.93 (br. dm (br. sept), 1JHC = 160.5 Hz, 5JFCCCCC = 1.9 76.94 (dt (s), JHC = 146.8 Hz, JHC
= 4.0 Hz, C ). 13С-{1H}
1
3
3
3
14,18
CC
Hz, C24), 127.76 (dm (s), JHC = 160.7 Hz, JHCCC = 6.0-7.0 Hz, NMR (100.6 МHz, СDCl3),
δ
C: 199.15 (br. dt (s), 2JHC = 3.3 Hz,
1
3
3
4
C
C15,17), 127.13 (br. dd (s), JHC = 161.4 Hz, JHCCC = 7.3 Hz, C21),
JHC
JHC
JHC
JHC
JHC
= 3.3 Hz, C4), 139.20 (tdd (s), JHC
= 7.3 Hz,
1
3
3
2
3
3
3
3
20,24
4
15,17 13
CC
CC
126.90 br. dm (br. q), JHC = 160.5 Hz, JFCCCCC = 5.0 Hz, C20),
= 5.5 Hz, JHOCC = 2.2 Hz, C13), 133.74 (br. t (s),
1
5
3
3
13
13
C
122.40 (qd (qd), 1JFС = 286.4 Hz, 3JPOCC = 8.6 Hz, CF3), 121.08 (qd
= 7.7 Hz, C19), 134.07 (br. td (s), JHC = 162.2 Hz,
1
21,23 19
CC
22
1
(qd), JFС = 289.4 Hz, JPOCC = 2.7 Hz, CF3), 83.41 (sept (sept),
3
22 = 7.7 Hz, C22), 129.33 (ddddd (s), 1JHC20,24 = 160.7 Hz,
20,24
CC
2JCCF = 29.3 Hz, C5), 82.93 (m(d), JPOC = 2.2 Hz, JHCC = 3.6 Hz,
= 1.4
15,17
2
2
3
= 7.6 Hz, JHC
2
= 7.6 Hz, JHC
24,20 20,24
CC
22 20,24
21,23 20,24
CC
C
3
4
1
JHCCC = 3.8 Hz, C7eq), 82.47 (dm (dq), 1JHC = 154.8 Hz, 2JPOC = 2.9 Hz, JHC
= 1.2 Hz, C20,24), 129.30 (br. dd (s), JHC
=
4
20,24
CCC
Hz, 4JFCCCC = 2.6-2.8 Hz, C3), 79.74 (dt (d), 2JPOC = 20.2 Hz, 3JHCCC
=
=
= 6.5-7.0 Hz, C15,17), 128.86 (dd (s),
3
161.0 Hz, JHC
15,17 17,15
CC
3.7 Hz, C4), 79.30 (m(d), JPOC = 2.9 Hz, JHCC = 3.7 Hz, JHCCC
JHC
= 7.7 Hz, C21,23), 128.76 (dtt
2
2
3
1
3
= 162.5 Hz, JHC
21,23
23,21 21,23
CC
3.6-3.7 Hz, C8ax), 23.72 (qdq (d), JHC = 127.6 Hz, 3JPOCC = 6.2 Hz, (s), JHC = 161.0 Hz, JHC
= 1.5 Hz,
1
1
3
2
= 7.2 Hz, JHC
16
14,18 16
15,17 16
CC
C
8 | J. Name., 2012, 00, 1-3
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3
= 162.4 Hz, JHC
C16), 127.96 (dm (s), 1JHC
= 6.5-7.5 20 hours (control by 31P NMR). 31Р/ 31Р-{1H} NMR (161.9 МHz,
14,18
18,14 14,18
CC
3
Hz, JHC
3
= 6.5-7.5 Hz, JHC
3
= 4.5 Hz, C14,18), 76.42 dioxane / δР (ppm): –1.2 (d (s), JPССH = 5.6 Hz), 14.0 (br. s (s)).
16 14,18
3
14,18
CC
CC
3 = 3.4 Hz, 2JHOC3 = 1.5 Hz, C3). 19F NMR (376.4 MHz, CDCl3) / F (ppm): –67.39 (q, 4JFCCCF = 10.9
δ
3
(dtd (s), 1JHC3 = 146.8 Hz, JHC
14,18
CC
Hz), –68.65 (q, 4JFCCCF = 10.9 Hz), –68.65 (q, 4JFCCCF = 10.9 Hz), –
4
Hydrolysis of compound 14. To the suspension of compound 69.98 (q, JFCCCF = 9.5 Hz). After completing of hydrolysis the
14 (3.54 g, 6.75 mmol) in 10 mL of diethyl ester a solution of reaction mixture was evaporated in vacuo (14 Torr) to give a
0.12 mL (6.75 mmol) of water in 5 mL of diethyl ester was yellow oily residue, which was crystallized from CH2Cl2 (10 mL).
added dropwise with constant stirring. The resulting white The crystalline precipitate of 18 (adduct with pinacol) was
crystalline precipitate of compound 16 was filtered off and filtered off and dried in vacuo (14 Torr). Yield 1.01 g (63 %), mp
dried in vacuo (14 Torr). Yield 3.01 g (82 %), mp 155-156°С. 99-103°С. Anal. Calcd. for C23H29F6O8P (578.44): С, 47.76; Н,
Anal. Calcd. for C23H25F6O6P (542.41): С, 50.93; Н, 4.65; Р, 5.71. 5.05; Р, 5.35. Found: С, 47.74; Н, 5.00; Р, 5.31. IR (nujol) (νmax
,
Found: С, 50.94; Н, 4.60; Р, 5.73. IR (nujol) (νmax, cm–1): 3606, cm–1): 3524, 3499, 3282, 3068, 2349, 1736, 1681, 1601, 1497,
3214, 2993, 1498, 1451, 1397, 1385, 1262, 1225, 1206, 1145, 1452, 1377, 1277, 1213, 1154, 1111, 1074, 1022, 1001, 967,
1
1134, 1006, 993, 962, 930, 910, 815, 806, 724, 713, 700, 616, 935, 761, 727, 711, 699, 624, 612, 541, 523, 494,463. Н NMR
594, 549, 497, 414. 1Н NMR (400 MHz, DMF-d7) / δ (ppm): 8.74 (400 MHz, CD3CN) / δ (ppm): 7.46 (br. d, 2H, Н20,24), 7.21 (d,
3
(br. s, 1H, OH), 7.60 (d, 2H, JHССН 5.6 Hz, Н20,24), 7.23 (m, 2H, 3JНССН = 7.1 Hz, 2H, Н14,18), 7.10 (m, 3H, Н19,20,21), 7.04 (m, 3H,
3
3JНССН = 6.7-7.7 Hz, 5JРСССCН = 1.5 Hz, Н14,18), 7.11 (m, 3H, Н21-23),
Н
15,16,17), 6.09 (d, JPOCH = 4.9 Hz, 1H, H3), 1.16 (s, 12H, Me,
7.05 (m, 3H, Н15-17), 6.25 (d, 1H, 3JPOCH = 7.6 Hz, H3), 5.98 (s, 1H, pinacol). 13C / 13С-{1H} NMR (100.6 МHz, CD3CN) / δC (ppm):
2
3
OH), 1.49 (s, 3H, Me), 1.42 (s, 6H, Me), 1.26 (s, 3H, Me). 13C / 137.98 (br. td (s), JHCC = 5.5, C19), 137.07 (br. td (br. s), JHCCC
13С-{1H} NMR (100.6 МHz, DMF-d7) / δC (ppm): 139.45 (br. td 7.3 Hz, C13), 131.10 (br. d (s), JHCCC = 156.6 Hz, C14,18),
∼
127.9
1
(br. s), JHCCC = 6.2, JHCC = 5.2, C13), 138.09 (ddd (s), JHCCC = 7.2 (v. br. d (v. br. s) C20, 24), 128.71 (br. dt (s), JHC 161.4 Hz, C16),
3
2
3
1
3
3
1
1
1
Hz, JHCCC = 6.7 Hz, JHCCC = 3.7 Hz, C19), 130.91 (dddd (s), JHC
=
128.64 (br. dt (s), JHC 161.7 Hz, C22), 128.10 (br. dd (s), JHC
=
163.3 Hz, JHCCC = 5.4 Hz, JHCCC = 5.2 Hz, JHCCC = 5.2 Hz, C14,18), 158.5 Hz, 3JHCCC = 7.3 Hz, C15,17), 127.85 and 126.74 (two v. br. d
3
3
3
1
1
∼
129.2 (v. br. d (v. br. s) C20), 128.53 (dt (s), JHC = 160.0 Hz, (two v. br. s), C20,24 and C21,23), 124.35 (q (q), JFC = 289.4 Hz,
3JHCCC = 7.4 Hz, C16), 128.13 (dt (s), JHC = 160.0 Hz, JHCCC = 7.7 CF3), 124.18 (q (q), JFC = 290.9 Hz, CF3), 90.34 (m (s), pinacol),
1
3
1
Hz, C22), 127.69 (br. dd (s), JHC = 161.8 Hz, JHCCC = 5.0-6.0 Hz, 83.79 (sept (sept), JFCC = 25.7 Hz, C5), 83.12 (d. m (d), JHС
=
1
3
2
1
C15,17), 127.37 (v. br. d (v. br. s), 1JHC
∼
160.0-162.0 Hz, C21,23,24), 151.5 Hz, JРOС = 2.6 Hz, C3), 81.87 (m (d), JРOCС = 8.1 Hz, C4),
2
3
124.80 (q (q), JFC = 291.6 Hz, CF3), 124.58 (q (q), JFC = 291.1 25.16 (q (s), JHC = 125.4, CH3, pinacol). 19F NMR (376.4 MHz,
1
1
1
Hz, CF3), 89.33 (m (d), JPOC = 1.2 Hz, C7 or C8), 89.23 (m (s), C8 CDCl3/DMSO-d6 (3:1)) / δF (ppm): –67.05 (q, JFCCCF = 11.2 Hz),
2
4
or C7), 83.34 (sept (sept), 2JFCC = 25.6 Hz, C5), 82.89 (br. dm (br. –67.82 (q, JFCCCF = 10.2 Hz). 31Р/ 31Р-{1H}NMR (161.9 МHz,
4
1
2
3
d), JHС = 149.5 Hz, JРOС = 5.1 Hz, C3), 81.75 (br. d (d), JРOCС
=
CD3CN) / δР (ppm): –1.4 (br. s (s)).
10.0 Hz, C4), 24.76, 24.27, 24.14 and 23.97 ppm (four qdq (four
d), 1JHC = 127.5, 127.5, 127.8 and 127.9 Hz, 3JPOCC = 4.4, 7.0, 3.9 Crystal structure determination. Crystal structures were
and 6.5 Hz, JHCCC = 4.3-4.4 Hz, C9-12). 19F NMR (376.4 MHz, determined by X-ray diffraction of suitable monocrystals.
3
4
DMF-d7) / δF (ppm): –67.43 (q, JFCCCF = 11.3 Hz), –68.19 (q, Crystal data were collected at 296
K
using graphite
-scan. Data
4JFCCCF = 11.3 Hz). 31Р/ 31Р-{1H} NMR (161.9 МHz, DMF-d7) / δР monochromatic MoKα (0.71073 Å) radiation and
ω
(ppm): 11.0 (d (s), JPССH = 5.9 Hz). 13C / 13С-{1H} NMR (100.6 collection images were indexed, integrated, and scaled using
3
МHz, DMSO-d6) / δ
C (ppm): 139.45 (br. td (br. s), C13), 137.0 (m the APEX2 data reduction package.46 Multi-scan empirical
(s), C19), 129.63 (dddd (s), JHCCC = 160.0 Hz, JHCCC = 6.0-7.0 Hz, absorption corrections were applied to all data sets, where
1
3
3JHCCC = 6.0-7.0 Hz, 3JHCCC = 4.4 Hz, C14,18),
∼
129.2 (v. br. d (v. br. appropriate, using the program SADABS.47 The structures were
s) C20), 127.65 (dt (s), JHC = 160.0 Hz, JHCCC = 7.3 Hz, C16), solved and refined using SHELX48 program. All pictures of
1
3
127.28 (dt (s), JHC = 160.0 Hz, JHCCC = 7.7 Hz, C22), 126.81 (dd crystal structures were created using Mercury CSD 2.4 49
.
1
3
(s), 1JHC = 160.0 Hz, 3JHCCC = 6.6 Hz, C15,17),
∼126.9 (v. br. d (v. br.
s), 1JHC
∼
160.0-162.0 Hz, C21,23,24), 124.68 (q (q), 1JFC = 292.0 Hz, Crystal data for 13. C23H23F6O5P,
M
= 524.38, monoclinic,
a
=
=
CF3), 123.45 (q (q), 1JFC = 290.5 Hz, CF3), 89.31 (m (s), C7 or C8), 9.485(6),
b
= 11.002(7),
c
= 12.115(8) Å,
β
= 101.517(8)
°
,
V
2
88.18 (m (s), C8 or C7), 82.01 (sept (sept), JFCC = 25.6 Hz, C5), 1239(1) Å3,
T
= 296 K, space group
P
21 (no. 4),
Z
= 2, 12827
81.29 (br. dm (br. d), JHС = 149.0 Hz, JРOС = 4.8 Hz, C3), 80.59 reflections measured, 4529 unique (Rint = 0.071), which were
1
2
(br. d (d), JРOCС = 9.9 Hz, C4), 24.24, 23.72, 23.55 and 23.37 used in all calculations. Final indices R1 = 0.0667, wR2 = 0.1629
3
1
(four qdq (four d), JHC = 127.6, 127.6, 128.4 and 129.1 Hz, for 2921 reflections with I > 2σ(
I); R1 = 0.1100, wR2 = 0.2021 for
3
3JPOCC = 3.7, 7.0, 3.3 and 6.2 Hz, JHCCC = 3.0-3.3 Hz, C9-12). 19F all data.
4
NMR (376.4 MHz, DMSO-d6) / δF (ppm): –66.49 (br. q, JFCCCF
=
10.9 Hz), –68.10 (br. q, JFCCCF = 10.9 Hz). 31Р / 31Р-{1H} NMR Crystal data for 14. C23H23F6O5P,
M
= 524.38, orthorhombic,
= 22.988(9) Å,
= 4855(3) Å3,
296 K, space group Pbca (no. 61),
measured, 4766 unique (Rint = 0.066), which were used in all
Hydrolysis of compound 16. Compound 16 (1.50 g, 2.77 mmol) calculations. Final indices R1 = 0.0520, wR2 = 0.1426 for 2856
a
4
3
(161.9 МHz, DMSO-d6) / δР (ppm): 10.7 (d (s), JPССH = 7.8 Hz). = 12.650(5),
b
= 16.695(6),
c
V
T
=
MALDI-MS (m/z): 565.03 (M + Na), 580.93 (M + K).
Z = 8, 28292 reflections
was refluxed in solution (15 mL) of dioxane and H2O (2 : 1) for reflections with I > 2σ(
I
); R1 = 0.0985, wR2 = 0.1825 for all data.
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Journal Name
1
2
K. N. Allen and D. Dunaway-Mariano, Trends Biochem. Sci.,
2004, 29, 495.
L. W. Tremblay, G. Zhang, J. Dai, D. Dunaway-Mariano and K.
N. Allen, J. Am. Chem. Soc., 2005, 127, 5298.
A. C. Hengge, Adv. Phys. Org. Chem., 2005, 40, 49.
J. K. Lassila, J. G. Zalatan and D. Herschlag, Annu. Rev.
Biochem., 2011, 80, 669.
N. J. Baxter, M. W. Bowler, T. Alizadeh, M. J. Cliff, A. M.
Hounslow, B. Wu, D. B. Berkowitz, N. H. Williams, G. M.
Blackburn and J. P. Waltho, PNAS., 2010, 107, 4555.
H. Gu, S. Zhang, K.-Y. Wong, B. K. Radak, T. Dissanayake, D. L.
Kellerman, Q. Dai, M. Miyagi, V. E. Anderson, D. M. York, J. A.
Piccirilli and M. E. Harris. PNAS., 2013, 110, 13002.
N. J. DeYonker and C. E. Webster, Biochem., 2015, 54, 4236.
G. Baccolini, Phosphorus, Sulfur, Silicon. Relat. Elem., 2015,
190, 2173.
Crystal data for 15. C6H15O5P,
M
= 198.15, orthorhombic,
= 995(4) Å3,
= 296 K,
= 4, 5025 reflections measured,
int = 0.068), which were used in all calculations.
Final indices R1 = 0.0499, wR2 = 0.1437 for 1316 reflections
with I > 2σ( ); R1 = 0.0907, wR2 = 0.1841 for all data.
a =
6.39(2),
space group
1949 unique (
b
= 10.62(3),
c
= 14.67(3) Å,
V
T
P
212121 (no. 19),
Z
R
3
4
I
5
6
Crystal data for 16. C23H25F6O6P,
10.788(13), = 10.889(13), = 12.329(15) Å, α = 70.63(2),
71.74(2), γ = 67.88(2)
= 1236(3) Å3,
P-1 (no. 2), = 2, 4706 reflections measured, which were used
in all calculations. Final indices R1 = 0.0880, wR2 = 0.2734 for
M
= 542.40, triclinic,
a
=
b
c
β
=
°
,
V
T = 296 K, space group
Z
7
8
2147 reflections with I > 2σ(
data.
I); R1 = 0.1946, wR2 = 0.3522 for all
9
M. A. van Bochove, M. Swart and F. M. Bickelhaupt, J. Am.
Chem. Soc., 2006, 128, 10738.
10 M. A. van Bochove, M. Swart and F. M. Bickelhaupt,
ChemPhysChem., 2007, , 2452.
11 S. Dey, Amer. J. Org. Chem., 2015,
12 Best Synthetic Methods: Organophosphorus (V) Chemistry.
Ed by C. Timperley. Elsevier, ISBN: 9780080982120, 2015.
13 W. Phakhodee, S. Wangngae and M. Pattarawarapan, RSC
Crystal data for 18. C17H15F6O6P · 0.5 C6H14O2,
M
= 519.34,
= 8.706(4) Å,
T = 296 K, space group P21/c (no.
8
monoclinic,
95.489(8)
14),
0.152), which were used in all calculations. Final indices R1
a
= 18.721(8),
b
= 13.944(6),
c
β =
5
, 83.
°,
V
= 2262(2) Å3,
Z
= 4, 11470 reflections measured, 4448 unique (Rint
=
=
=
Adv., 2016, 6, 60287.
14 P. A. Byrne and D. G. Gilheany, Chem. Soc. Rev., 2013, 42
0.0773, wR2 = 0.1632 for 1683 reflections with I > 2σ(
0.2229, wR2 = 0.2372 for all data.
I); R1
,
6670.
15 D. J. Carr, J. J. S. Kudavalli, K. S. Dunne, H. Müller-Bunz and D.
G. Gilheany, J. Org. Chem., 2013, 78, 10500.
Conclusions
16 E. V. Jennings, K. Nikitin, Y. Ortin and D. G. Gilheany, J. Amer.
Chem. Soc., 2014, 136, 16217.
It was shown that the reaction of 4,4,5,5-tetramethyl-2-(2-oxo-
1,2-diphenyl)ethoxy-1,3,2-dioxaphospholane 12 with
17 K. C. Kumara Swamy, N. N. Bhuvan Kumar, E. Balaraman and
K. V. P. Pavan Kumar, Chem. Rev., 2009, 109, 2551.
hexafluoroacetone results in simultaneous formation of 18 (a) S. Fletcher, Org. Chem. Front., 2015,
2, 739; (b) D. Camp,
M. von Itzstein and I. D. Jenkins, Tetrahedron, 2015, 71
4946.
,
regioisomeric cage (P–C/P–O)-phosphoranes 13
, 14 in ratio of
10 to 1. In dichloromethane solution (20°C, 5 days) the
19 S. Wangngae, C. Duangkamol, M. Pattarawarapan and W.
Phakhodee. RSC Adv. 2015, , 25789.
rearrangement of P–C-isomer 13 to the P–O-isomer 14
proceeds with a high stereoselectivity (> 96 %). The P–C-
isomer hydrolysis unexpectedly leads to the formation of 2-
hydroxy-4,4,5,5-tetramethyl-2-oxo-1,3,2-dioxaphospholane
with a high chemoselectivity. Hydrolysis of P–O-isomer results
in the formation of one stereoisomer of 2-(2,3-dihydroxy-1,2-
diphenyl-3-trifluoromethyl-4,4,4-trifluorobutyloxy)-4,4,5,5-
tetramethyl-2-oxo-1,3,2-dioxaphospholane with the same
configurations of C3 and C4 atoms; further hydrolysis of this
5
20 S. Cao, P. Gao, Y. Guo, H. Zhao, J. Wang, Y. Liu and Y. Zhao, J.
Org. Chem., 2013, 78, 11283.
21 W. Dai, Q. Liu, X. You, Z. Zhou, Y. Guo, Y. Zhao and S. Cao,
Heteroatom Chem., 2016, 27, 63.
22 X. You, L. Qi, J. Zheng, W. Dai, Y. Guo, Y. Zhao and S. Cao,
Heteroatom Chem. 2015, 26, 168.
23 J. Bader, N. Ignat'ev and B. Hoge, Inorg. Chem., 2014, 53
7547.
,
24 S. M. McCarthy, Y.-C. Lin, D. Devarajan, J. W. Chang, H. P.
Yennawar, R. M. Rioux, D. H. Ess and A. T. Radosevich, J. Am.
Chem. Soc., 2014, 136, 4640.
25 O. Fliss, A. Mejri, K. Essalah, M.-T. Boisdon and B. Tangour,
Compt. Rend. Chim., 2016. DOI: 10.1016/j.crci.2015.11.007.
26 N. V. Ignat’ev, J. Bader, K. Koppe, B. Hoge and H. Willner. J.
Fluor. Chem., 2015, 171, 36.
27 R. Pajkert and G.-V. Röschenthaler, Pentacoordinated and
hexacoordinated compounds. Ch. 8. Organophosphorus
Chem., 2015, 378-396.
compound
yields
2,3-dihydroxy-3-trifluoromethyl-4,4,4-
trifluoro-1,2-diphenyl butylphosphate 17 and pinacol.
Acknowledgements
Financial support from the Russian Foundation for Basic
Research (Grant No. 16-03-00451) is gratefully acknowledged.
28 (a) R. R. Holmes, Pentacoordinated Phosphorus – Structure
and Spectroscopy (ACS Monograph 175), Am. Chem. Soc.,
Washington, DC, 1980. (b) R. R. Holmes, Pentacoordinated
Phosphorus – Reaction Mechanisms (ACS Monograph 176),
Am. Chem. Soc., Washington, DC, 1980.
29 D. E. C. Corbridge, Phosphorus 2000. Chemistry, Biochemistry
and Technology, Elsevier, Amsterdam – Lausanne – New-
York – Oxford – Shannon – Singapore – Tokyo, 2000, ISBN:
0444825509.
Notes and references
‡ Crystallographic data (excluding structure factors) for these
structures 13-16, 18 have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC 1474601-1474604, 1485824 respectively. Copies of the
data can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223/336-033; E-
mail: deposit@ccdc.cam.ac.uk).
30 L. M. Abdrakhmanova, V. F. Mironov, T. A. Baronova, M. N.
Dimukhametov, D. B. Krivolapov, I. A. Litvinov, A. A.
10 | J. Name., 2012, 00, 1-3
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Balandina, Sh. K. Latypov and A. I. Konovalov, Mendeleev
Commun., 2006, 16, 320.
31 L. M. Abdrakhmanova, V. F. Мironov, T. P. Gryaznova, S. A.
Katsyuba and M. N. Dimukhametov, Phosphorus, Sulfur,
Silicon. Relat. Elem., 2011, 186, 652.
32 V. F. Mironov, M. N. Dimukhametov, E. V. Mironova, D. B.
Krivolapov and L. M. Abdrakhmanova, Russ. J. Gen. Chem.,
2015, 85, 441.
33 V. F. Mironov, M. N. Dimukhametov, E. V. Mironova, D. B.
Krivolapov, G. A. Ivkova and L. M. Abdrakhmanova, Russ. J.
Gen. Chem., 2015, 85, 450.
34 V. F. Mironov, T. A. Baronova, E. V. Mironova, M. N.
Dimukhametov, D. B. Krivolapov and L. M. Abdrakhmanova,
Russ. J. Org. Chem., 2015, 51, 401.
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