4-Dimethylaminopyridine-catalyzed dynamic kinetic resolution in asymmetric synthesis of P-chirogenic 1,3,2-oxazaphospholidine-2-oxides

Article abstract of DOI:10.1039/c6ra16686e

Excellent diastereoselectivity (dr value up to 100: 0) was achieved in DMAP-catalyzed P-N bond formation in the synthesis of P-chirogenic organophosphines from phenylphosphonic dichloride (PhP(O)Cl₂) and (S)-2-pyrrolidinemethanol derivatives. I

Full text of DOI:10.1039/c6ra16686e

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4-Dimethylaminopyridine-catalyzed Dynamic Kinetic Resolution in
Asymmetric Synthesis of P-Chirogenic 1,3,2-Oxazaphospholidine-
2-Oxides
Received 00th January 20xx,
Accepted 00th January 20xx
Lanlan Wang,a, b Shanshan Cao,c Zhijun Du,a Qiang Wu,a, b Zheng Bian,a Chuanqing Kang,*a Lianxun
Gaoa and Jingping Zhangc
DOI: 10.1039/x0xx00000x
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Excellent diastereoselectivity (dr value up to 100:0) was achieved in DMAP-catalyzed P-N bond formation in the synthesis
of P-chirogenic organophosphines from phenylphosphonic dichloride (PhP(O)Cl2) and (S)-2-pyrrolidinemethanol
derivatives. Investigations with NMR spectra and calculations revealed the formation of a bimolecular complex from
(PhP(O)Cl2) and revealed DMAP as an ‘active phosphonyl’ that was converted to the P-N bonded compound with
significant preference for one of two diastereomers through dynamic kinetic resolution. These results present for the first
time the mechanism of conversion from an achiral phosphorus centre to a P-stereogenic centre by direct stereoselective
reaction at the phosphorus centre.
by modification of the carbonyl skeleton linked to a prochiral
phosphorus centre.5 We have recently established an
Introduction
organocatalytic synthesis of phosphoramides with
a P-
Optically pure P-chirogenic organophosphorus compounds
have become an active research interest with steady growth in
the past two decades.1 The distinctive geometry around the P-
stereogenic centre, unlike C-centre, provides a criterion for
chiral information transfer in organic conversion, polymeric
conformation and supramolecular assemblies.2 Successful
applications of P-chiral organophosphines as organocatalysts
or as ligands for metallocatalysis have spurred intensive
research on these compounds, in particular, on the synthesis
of P-chirogenic catalytic scaffolds.3 Strategies for this synthesis
include chiral skeletal modification, catalytic asymmetric
synthesis, and thermodynamic or kinetic resolution. Limited
chiral pools including ephedrine, menthanol and prolinols have
been used for inducing diastereoselective reaction at the P-
centre.4 In those reactions, separation is usually unavoidable
for accessing optically pure products. Ephedrine was most
effective for inducing high stereoselectivity, however it is not
commercially available due to possible abuse as a drug.
Catalytic enantioselective synthesis has more potential and is
attractive because of the nature of high efficiency and less
reagent consumption, but it remains limited achievements
from metallocatalytic kinetic resolution or desymmetrization
chirogenic center as the sole chiral centre with moderate
enantioselectivity,6 demonstrating the biggest challenge in the
formation of P-chirogenic centres: direct modification of an
achiral phosphorus centre.7 The activation of a phosphorus
substrate and the interaction of the phosphorus substrate with
a carbon-based chiral framework during chiral induction are
not well studied.
In our research on the synthesis and application of P-chiral
compounds, we are interested in the stereoselectivity and
mechanism of the formation of P-chirality induced by C-
chirality, which is believed to be on an approach to address the
challenge in enantioselective synthesis of P-chiral phosphorus
compounds. We selected P-chiral 1,3,2-oxazaphospholidine-2-
oxides
3 containing P(V)-chiral centres as our primary subject
because of their potential in catalysis and as precursors for
other organophosphorus compounds.4, 8 With this model, we
have gained deep insight into the asymmetric formation of P-N
and P-O bonds in the synthesis of
3 from 1 and the prolinols 2.
In previous reports of this synthesis, low to moderate
diastereoselectivity was obtained without the presence of
DMAP
(Scheme
1).4a-d
In
this
work,
excellent
diastereoselectivity was achieved in scalable conditions with
DMAP as catalyst and the mechanism was studied. Crich has
used DMAP in reactions at the P(III)-centre of P-chiral
phosphonosugars,
showing
improvement
of
diastereoselectivity.9 To the best of our knowledge, no such
reaction on P(V)-centre has yet been described.
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Journal Name
Entry
1
R
X
0
Yieldb
drc
R
R
R
R
O
P
Ph (2a)
79%
51%
56%
68%
72%
65%
78%
99%
85%f
79%
93%
86%
81%
75%
65%
75%
89%
87:13
91:9
conditions
OH
2
10
20
25
30
40
50
30
30
30
80
100
110
0
O
+
Cl
Cl
Ph
N
3
92:8
NH
P
4
96:4
Ph
O
1
2a (R = Ph)
2b (R = H)
5
100:0
100:0
100:0
100:0
100:0
79:21
97:3
3a (R = Ph)
3b (R = H)
6
conditions and results
7
Reported: Et3N, CH2Cl2, 0 oC, dr up to 87:13 for 3a, 63:37 for 3b
This work: DMAP, Et3N, CH2Cl2, r.t., dr 100:0 for 3a, 75:25 for 3b
DMAP, imidazole, CH2Cl2, r.t., dr 91:9 for 3b
8d
9e
10g
11g
12g
13g
14
15
16
17h
Scheme 1 Synthesis of 3 with DMAP as organocatalyst
93:7
83:17
63:37
75:25
75:25
90:10
Results and discussion
H (2b)
30
80
50
The initial attempt for the reaction of 1 (1.5 eq) and 2a (1.0 eq)
in dichloromethane (DCM) yielded 3a with consistent
diastereoselectivity (dr 87:13) according to the literature,4a as
determined by 1H NMR spectroscopy (entry 1, Table 1). The
reaction afforded same diastereoselectivity in chloroform and
lower diastereoselectivity in toluene but did not proceed in
THF or DMF (see Table S1, ESI). Surprisingly, an improvement
in the diastereoselectivity to dr 91:9 was observed for the
reaction in DCM by using DMAP (10 mol% based on 2a) as an
organocatalyst (entry 2, Table 1). The dr value was increased
with higher DMAP loading and reached to 100:0 when a
minimum of 30 mol% DMAP was used (entries 3 to 7, Table 1).
Longer reaction times increased the yield (entry 8, Table 1).
Gram-scale synthesis of (RP)-3a under optimized conditions
afforded an isolated yield of 85% from crystallization (entry 9,
a Reaction conditions: 1 (0.3 mmol, 1.5 eq, otherwise indicated), 2 (0.2 mmol),
triethylamine (0.6 mmol) otherwise indicated, DMAP (X mol%), CH2Cl2 (2 ml), r.t.,
10 h otherwise indicated; b Of major isomer determined by 1H NMR; c (RP)-3:(SP)-
3, determined by 1H NMR; d Reaction time: 24 h; e Starting with 2 g of 2a; f
Isolated yield from crystallization. g 0.22 mmol (1.1 eq) of 1 used. h Imidazole as
base and see ESI for more details.
The DMAP-facilitated diastereoselectivity of the synthesis of
1
was monitored by H NMR. Two groups of aromatic proton
3
signals belonging to the pyridyl group of DMAP and the phenyl
group of were observed in a mixture of and DMAP, which
were assigned to DMAP trapped in rac- and rac- (Figure 1).
The later was derived from the complexation of rac- and
another molecule of DMAP. The observations of unique APh
signals for the mixtures of DMAP and at molar ratios of 1:1.5
and 0.3:1.5 suggested the presence of rapid interconversations
between , DMAP and rac- (Figure S2, ESI). rac- was the sole
complex observed by 1H NMR when DMAP and
were at a
1
1
A
B
A
Table 1). We also attempted to reduce the amount of
1 used in
the reaction. However, a lower dosage of 1 (1.1 eq) led to a
1
decrease in the diastereoselectivity (Entry 10, Table 1). More
experiments showed that too much DMAP did not always
improve the diastereoselectivity (entries 11 to 13, Table 1). In
the case of 2b as the reaction substrate, 30 mol% DMAP
improved dr from 63:37 to a maximum 75:25 (entries 14 to 16,
Table 1). The dr value of the product 3b increased to 91:9
when triethylamine was replaced with imidazole and 100
1
A
B
1
molar ratio of 2:1. The results suggested the presence of a
rapid dynamic equilibrium by interconversion between both
enantiomers of P-chiral rac-A through exchanges of chloride
and DMAP at the P-centre.9, 10
mol% DMAP was used (entry 17, Table 1). The absolute
1
was confirmed by H
configuration of the P-chiral centre of
NMR and 2D NOESY.4a-b
3
Table 1 Conditions Optimization for Synthesis of 3a
R
R
R
R
R
R
1, Et3N
O
+
O
OH
DMAP (X mol%)
CH2Cl2
r.t., 10 hr
N
N
P
P
NH
Ph
Ph
O
(RP)-3
O
(SP)-3
2
Figure 1 The interconvsions in a mixture of 1 and DMAP and corresponding 1H NMR.
Proton signals APy and APh were from protons on pyridyl and phenyl trapped in balance
between DMAP, 1 and rac-A. Proton signals BPy and BPh were from protons on pyridyl
and phenyl of rac-B.
2 | J. Name., 2012, 00, 1-3
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overlapped; however, this was not observed for the Hb signals
(δ3.63 and δ3.12 ppm, the latter was obscured by
triethylamine signals). Thus, the integral ratio of Ha/(Ha - Hb)
was used to estimate the dr values of
the signals of Ha and Hb of and (RP)-3a maintained an integral
of 1:1 suggested the presence of single diastereoisomer of
both
and 3a during the course of the reaction. The 31P NMR
C and 3a. The fact that
C
C
monitor to the reaction showed consistent results that single
diastereomer was observed during the whole reaction time
(Figure S5, SI). Therefore, single stereoselectivity at the P-
centre was determined at the stage from rac-
enantiomer of was exclusively produced from 2a by kinetic
stereoselectivity, with a highly matched geometry of 2a and
one enantiomer of rac- . The rapid dynamic equilibrium
between enantiomers of rac- or those of subsequent
transition states result in the catalytic conversion of another
enantiomer of rac-
A to C. One
C
A
A
A
.
In another control experiment without using triethylamine
was observed the formation of (RP)-3a in less than 40% yield
1
according to H and 31P NMR track of the reaction (Figure S6
Figure 2 1H NMR trace of the reaction between 1 and 2a in CD2Cl2 in the presence of
DMAP. BPh and BPy were the proton signals of phenyl and pyridyl of rac-B, respectively.
CPys were the proton signals of pyridyl of presumed intermediate C, while Ha and Hb
were the proton signals on pyrollidino cycle of C as indicated in the inset.
and S7, SI). An unspecified intermediate was observed and
converted to (RP)-3a in 88% yield on addition of triethylamine
after 12 h of the reaction. Single enantiomer of unspecified
intermediate and (RP)-3a was observed during the whole
reaction period. The results strongly supported that
triethylamine was beneficial for the conversion while DMAP
was a determinative factor for the diastereoselectivity.
When 2a was added to a mixture of
1 and DMAP in DCM,
the proton signals of rac-A immediately disappeared, and no
1
signals of 2a were observed in the H NMR spectra (Figure 2).
A group of proton signals, CPy (δ8.18 and δ6.61 ppm), assigned
Further insights into the high stereoselectivity induced by
DMAP and the mechanism of the reaction were achieved by
computer modelling using the Gaussian 09 package, in which
the geometries were optimized with the B3LYP/6-31G(d, p)
basis set in the solvent phase.11 The reaction paths from both
to the pyridyl group of a presumed intermediate
these signals gradually weakened and finally completely
disappeared within 24 h, while the pyridyl signals (BPy) of rac-
C appeared;
B
were synchronously enhanced at a level corresponding to the
reduction of CPy. The DMAP released from the reaction was
enantiomers of rac-A were considered to identify the kinetic
trapped to form rac-B. DMAP in excess of 1 may result in the
elements of stereochemical preference in the formation of the
P-chiral centre. From the energy profiles (Figure 3), the
conversion from (SP)-C1 to (SP)-3a crossed two higher energy
barriers compared with that from (RP)-C1 to (RP)-3a. However,
these conversions should not be the determinative element
presence of free DMAP, which is not beneficial for improving
the stereoselectivity, as shown by experiments varying the
ratio of
Table 1). These results suggested that rac-
species that was converted to the presumed intermediate
1
and DMAP used in the reaction (entries 10 to 13,
A
was the reactive
1
C
for stereoselectivity because the H NMR data did not support
through P-N bonding and DMAP exchange prior to the
formation of the intramolecular P-O bond.
the presence of two epimers of C1 or C2
, or their
interconversions.
In the NMR spectra of the reaction, the signals of pyrrolidino
group Ha (δ4.72 ppm) of the diastereoisomers of either
C or 3a
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Figure 3 Free energy profile of processes from rac-A to both diastereomers of 3a, in which were shown only the structure of the intermediates and transition states toward (RP)-3a.
See ESI for complete energy profile with other intermediates and transition states.
The complexes (SP)-
the assembly of both (SP)-
reversible intermolecular
NH(2a)···Clˉ···HO(2a and PCl···NH(2a)···O(=P) (Figure 4).
Although (RP)- 2a was more stable than (SP)- 2a according to
A
·
2a and (RP)-
and (RP)-
hydrogen
A
·
2a were formed from
with 2a through
bondings of
Ph
Ph
OH
Ph
Cl
Cl
DMAP+
Ph
A
A
O
P
O
H
N
Cl-
Cl
Ph
Ph
N
P
H
Ph
O
DMAP+
P
)
O
Cl
A
(RP)-
A
·
A·
(RP)-A 2a
(SP)-C1
their ΔG values in the energy profile, the formation of the P-N
bond from the former to (SP)-C1 across the energy barrier
(ΔΔG = 14.9 kcal/mol) at the transition state of TS1S was
higher than that from the latter to (RP)-C1 (ΔΔG = 10.7
DMAP+
=
N+
NMe2
PhP(O)Cl2
Ph
Ph
OH
Cl
Cl
Cl
Ph
kcal/mol) at TS1R (Figure 3). Rapid consumption of (SP)-
the formation of the P-N bond resulted in a tendency of (RP)-
2a to dissociate to complement the decrease of 2a
Dissociated (RP)- would be converted to its enantiomer (SP)-
through the reversible balance of rac-
the DMAP-catalyzed dynamic kinetic resolution of rac-
A
·
2a in
O
P
O
H
N
Cl-
Ph
Ph
P
N
H
Ph
DMAP+
DMAP+
O
Cl
P
A
·
.
O
(SP)-A
Ph
(RP)-C1
A
A
(
SP
)-A 2a
A
with
1
or rac-
B
. Thus,
Scheme 2 Dynamic kinetic resolution of rac-A. DMAP of (SP/RP)-C1 was omitted for
would clarity.
A
be a key element to determine the high diastereoselectivity in
the conversion from 2a to (RP)-C1 (Scheme 2).12
The intermediate (RP)-C1 remained in complexation with
one DMAP molecule, which was converted to (SP)-C2 with the
replacement of a chloride on phosphoryl centre by DMAP
through the transition state TS2R with the energy barrier (ΔΔG
= 23.9 kcal/mol), the highest of all the steps. The formation of
the P-O bond in the conversion from (SP)-C2 to (RP)-3a went
through the transition state TS3R with another high-energy
barrier (ΔΔG = 18.6 kcal/mol). In the favorable pathway of the
(RP)-3a generation, the rate-determining step was the
nucleophilic addition of DMAP to the intermediate (RP)-C1
(
TS2R). In the 1H NMR traces of the reaction, the proton signals
assigned to the presumed intermediate were probably those
C
of (RP)-C1, which were indistinguishable in the NMR spectra.
Figure 4 3D diagrams of (SP)-A·2a and (RP)-A·2a and hydrogen bondings in the
Electrospray ionization mass spectrometry (ESI-MS) of the
complexes obtained from the calculations by B3LYP/6-31G(d, p).
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reaction mixture showed a molecular ionic peak with m/z energies reported here are in Kcal/mol, and bond lengths are
498.4, which supported the presence of the intermediate (RP)- in angstroms (Å).
C1 or (SP)-C2 (Figure S1, ESI).
Typical procedure for the synthesis of P-Stereogenic 1,3,2-
Oxazaphospholidine-2-oxides: DMAP (7.3 mg, 0.06 mmol, 0.3
equiv.) and a prolinol of 2a or 2b (0.2 mmol, 1.0 equiv.) were
dissolved in DCM (2.0 mL) in ice-water bath. Triethylamine (84
uL, 0.6 mmol, 3.0 equiv.) and PhP(O)Cl2 (42 uL, 0.3 mmol, 1.5
equiv) was added successively. The mixture was allowed to
warm to 25 oC and stirred for 10 h. After completion of the
reaction, DCM (5 mL) was added to the reaction mixture,
which was washed with saturated aq. NaHCO3 for three times.
The organic layer were then dried over MgSO4, filtered, and
tri(o-toluyl)phosphine was added as internal standard. The
resulting mixture was concentrated under reduced pressure.
The yield and the dr values were determined by 1H NMR.
Conclusions
In summary, we studied DMAP-catalyzed dynamic kinetic
resolution in the prolinol-induced formation of a P-chirogenic
centre during the synthesis of 1,3,2-oxazaphospholidine-2-
oxides 3 from phenylphosphonyl dichloride 1 and prolinols 2 as
a model reaction. The use of 30 mol% DMAP improved the
diatereoselectivity from 87:13 to 100:0 for the synthesis of 3a
and from 63:37 to 75:25 for the synthesis of 3b. Investigations
by NMR spectra and calculations revealed the formation of an
‘active phosphonyl’, rac-
key intermediate associated with 2a prior to the P-N bond
formation. The dynamic kinetic resolution of rac- through the
rapid consumption of (SP)- 2a, the reversible association of
with 2a and the interconversion between
determined the high diastereoselectivity in the Science Foundation of China (NSFC No. 21574126).
A, from 1 and DMAP. rac-A was the
A
Acknowledgements
A
·
rac-
A
A
1, DMAP and The authors appreciate financial support by National Natural
rac-
formation of the P-N bond. The nucleophilic addition of DMAP
to the intermediate (RP)-C1 TS2R) was the rate-determining
(
Notes and references
step, during which the P-N bonded intermediates C1 were
monitored by 1H NMR spectra. This study revealed for the first
time the mechanism of DMAP-catalyzed stereoselectivity in
the formation of P-N and P-O bonds at the achiral phosphorus
centre. These results would be valuable for the design of
organocatalyst to induce the formation of P-chirogenic centres
from achiral phosphorus precursors by direct asymmetric
reactions at the centres.
1
(a) A. Grabulosa, P-Stereogenic Ligands in Enantioselective
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Experimental
General information
: All reagents were obtained from
commercial sources and were used without further
purification. The NMR spectra were recorded on Bruker
1
Avance III with CD2Cl2 or CDCl3 as solvent. The H NMR were
recorded at 400 MHz or 300 MHz with TMS as internal
standard. The 13C NMR spectra were recoded at 100 MHz with
solvent as internal standard. The 31P NMR were recorded at
162 MHz with tri(o-toluyl)phosphine as internal standard. All
coupling constants (J values) were reported in Hertz (Hz). High
resolution mass spectra (HRMS) were measured using a Bruker
Autoflex III MALDI-TOF mass spectrometer. The purification of
products with column chromatography was performed on
silica gel with 100–200 mesh.
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by using the PCM solvation model. All charge distributions
were calculated by Natural Bond Orbital (NBO) analysis.
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nonessential hydrogen atoms are omitted for clarity. All
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DOI: 10.1039/C6RA16686E
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Excellent diastereoselectivity was achieved in DMAP-catalyzed P-N bonding in the synthesis of
P-chirogenic organophosphines through dynamic kinetic resolution.