Diastereoselective hydrolysis of asymmetric P-Cl species and synthesis of optically pure (RP)-(-)-menthyl H-phenylphosphinate

Article abstract of DOI:10.1002/ejoc.201500126

Phenyl dichlorophosphine reacted with (L)-(-)-menthol to afford two diastereomers of menthyl phenylphosphinate (R_P)-1a/(S_P)-1a′ in up to 89:11 dr. Compound (R_P)-1a was isolated in 58 % yield (60 g) and > 99:1 dr. An HCl-promoted diastereoselective hydrolysis of the P-Cl species was found to be involved in the reaction. On the basis of this, a mixture of 1a/1a′ with 50:50 dr was converted to a mixture enriched in 1a with 88:12 dr by treatment with phosphorus trichloride.

Full text of DOI:10.1002/ejoc.201500126

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201500126
Diastereoselective Hydrolysis of Asymmetric P–Cl Species and Synthesis of
Optically Pure (R )-(–)-Menthyl H-Phenylphosphinate
P
[a]
[a]
[a]
[b]
Wei-Min Wang, Li-Juan Liu, Chang-Qiu Zhao,* and Li-Biao Han*
Keywords: P Stereogenic / Phosphorus / Diastereoselectivity / Hydrolysis / Synthetic methods
Phenyl dichlorophosphine reacted with (L)-(–)-menthol to af-
ford two diastereomers of menthyl phenylphosphinate (R )-
a/(S )-1aЈ in up to 89:11 dr. Compound (R )-1a was isolated
stereoselective hydrolysis of the P–Cl species was found to
be involved in the reaction. On the basis of this, a mixture of
1a/1aЈ with 50:50 dr was converted to a mixture enriched in
1a with 88:12 dr by treatment with phosphorus trichloride.
P
1
P
P
in 58% yield (60 g) and Ͼ 99:1 dr. An HCl-promoted dia-
Introduction
workers from the reaction of PhPCl with (L)-(–)-menthol,
2
followed by hydrolysis of the intermediate with water.[
7]
P-Stereogenic phosphorus compounds are of high im-
portance either as biologically active substances or as pre-
cursors of chiral phosphine ligands that are widely used in
asymmetric catalysis.[1] However, acquisition of these com-
pounds in optically pure form usually involves tedious pro-
cesses such as kinetic resolution or the use of chiral auxilia-
ries. Although the configuration at the phosphorus center
can be completely retained or inverted during some reac-
tions, the initial generation of a chiral phosphorus atom
often gives unsatisfactory stereoselectivity,[ which results
in bottlenecks in the preparation and application of P-
stereogenic compounds.
Mislow and co-workers obtained a mixture enriched with
[8]
1a (1a/1aЈ ca. 95:5) by fractional recrystallization. There-
after, several preparations and applications of the com-
[4,9]
pound were reported.
Furthermore, 1a and analogues
have been obtained by the treatment of MenOPCl with
2
aryl Grignard reagents, followed by hydrolysis, resulting in
yields of around 30% of the diastereomerically pure prod-
[5,6,10]
uct.
Recently, Berger and Montchamp reported a
multi-step strategy to prepare 1a starting from hypophos-
2]
[11]
phorous acid, paraformaldehyde, and (–)-menthol.
A
straightforward and practical method suitable for the prep-
aration of optically pure P–H species in satisfactory yield
and on a ten-gram scale has scarcely been developed.
As relatively easily accessible compounds, chiral P–H
species attract considerable attention because of their vari-
[5]
When following Mislow’s procedure, we found optically
[
3]
ous applications in the construction of P–C bonds
through cross-coupling, substitution, or hydrophosphin-
pure 1a (Ͼ 99:1) could be obtained, but in quite poor yield.
Meanwhile, a mother liquor that contained 1a/1aЈ in near
[
4]
ylation. Among chiral P–H species, (R )-(–)-menthyl
P
1:1 dr was obtained. The yield of 1a depended upon the dr
phenylphosphinate (1a) is very commonly used due to the
ease with which various groups such as alkyl, vinyl or aryl
can be effectively introduced onto the chiral phosphorus
atom. Recently we reported the addition of 1a to C=O
of 1a/1aЈ when the two diastereomers were formed by the
hydrolysis of the intermediate P–Cl species. To the best of
our knowledge, the hydrolysis of such asymmetric P–Cl spe-
cies, including the stereochemistry and improvement of the
ratio of the two produced stereoisomers, has not been re-
ported in detail. Herein, we endeavored to reveal the
mechanism and thus to improve the ratio of 1a/1aЈ.
[
5a,5b]
bonds to form P-stereogenic α-hydroxy phosphinates.
Also, optically pure 1a was used as precursor of P-
[5c]
stereogenic secondary phosphine oxides, or directly as a
ligand for asymmetric hydrogenation.[
6]
A diastereomeric mixture of menthyl phenylphosphinate
(
R )-1a/(S )-1aЈ was first prepared by Letsinger and co-
P P
Results and Discussion
[
[
a] College of Chemistry and Chemical Engineering, Liaocheng
University,
In the presence of pyridine, (L)-(–)-menthol reacted with
PhPCl to form menthyl phosphorochloridite 2a. Hydroly-
Shandong 252059, China
2
E-mail: literabc@hotmail.com
sis of 2a in situ at low temperature selectively afforded 1a
and its epimer 1aЈ. As seen in Table 1, the best dr (85.5:14.5)
was obtained from the hydrolysis with water (Table 1, en-
try 1). Acidic, alkaline, and alcoholic additives for the
hydrolysis resulted in a decreased dr (Table 1, entries 4–7).
http://hgxyjxw.lcu.edu.cn/hxhgxy/cn/index.asp
b] National Institute of Advanced Industrial Science and
Technology (AIST),
Tsukuba, Ibaraki 305-8565, Japan
E-mail: libiao-han@aist.go.jp
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500126.
A poor dr was also observed when excess PhPCl was used
2
2342
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 2342–2345

Diastereoselective Hydrolysis of Asymmetric P–Cl Species
(Table 1, entries 2–3); in these cases more than 1 equiv. of
The reaction of PhPCl2 with (L)-(–)-menthol on a
HCl was generated during hydrolysis. When ethanol was 0.37 mol scale was carried out at –80 °C, and two dia-
used as an additive, free (L)-(–)-menthol was detected, stereomers 1a/1aЈ were formed in 80:20 dr. On this scale, 1a
which was probably formed from replacement of menthoxyl was isolated in 58% yield (60 g) from recrystallization with
with ethoxyl.
hexane at –30 °C. Meanwhile, the mother liquor that con-
tained 1a/1aЈ (ca. 1:1) was obtained in 39% yield. Total
yield of 1a, together with 1a/1aЈ, was near to quantitative.
2
Table 1. Formation of 1a/1aЈ from PhPCl and (L)-(–)-menthol.
Attempts to isolate (S )-1aЈ failed. It was clear that the iso-
P
lated yield of (R )-1a depended on the original ratio of 1a/
P
1aЈ.
Although the mechanism for hydrolysis of 2a remained
unclear, we can speculate some aspects based on the ap-
pearance of the reaction. Initially, 1a and 1aЈ were thought
to be directly formed from two stereoisomers of 2a, respec-
Entry Amount of PhPCl
2
Additives
1a/1aЈ[a]
tively. However, the 1:1 ratio of two peaks of 2a in the
31
P
NMR spectra, even at low temperature (–78 °C), indicated
that neither one of the two stereoisomers was dominant.
Capturing 2a also confirmed this observation. When PhSLi
was added to the solution of 2a, either at room temperature
or at –80 °C, O-menthyl S-phenyl phenylphosphonothioite
1
2
3
4
5
6
7
1.2
1.8
2.4
1.2
1.2
1.2
1.2
–
–
–
85.5:14.5
80:20
77:23
acetic acid
ethanol
pyridine
80:20
71:29[
b]
50:50[
c]
3
a/3aЈ was obtained in the ratio of 1:1, which was con-
firmed by the equal heights of peaks at δ = 146.7 and
50.5 ppm in the 31P NMR spectrum (Scheme 1). When
a peak at δ = 26.89 ppm in the 31P NMR spectra was formed in tert-butylmagnesium chloride was used, a mixture of tert-
conc. HCl
81:19
[
a] The 1a/1aЈ ratio was estimated by 31P NMR spectra. [b] Free
menthol was detected in 40%. [c] An unconfirmed compound with
1
25% yield.
butyl(menthoxy)phenylphosphine 3b/3bЈ was obtained in a
ratio of 64:36. The slight selectivity may be ascribed to the
Pure 2a could be isolated by distillation.[12] Two single steric hindrance of the bulky tert-butyl group. These results
peaks at δ = 175.14 and 178.15 ppm, in the ratio of 1:1, demonstrated that 1a/1aЈ were not formed directly from the
3
1
were observed on its P NMR spectra, which were assigned two stereoisomers of 2a.
as the two diastereomers derived from the R or S configura-
tion at phosphorus. Hydrolysis of isolated 2a confirmed the
dependence of dr on solvents, temperature, and other condi-
tions. As shown in Table 2, better selectivity was obtained
in diethyl ether. Either less or more polar solvents than di-
ethyl ether such as pentane, toluene, chloroform, and THF,
gave poorer dr. In diethyl ether, a 72:28 dr was obtained at
room temperature, and a higher dr of 89:11 was obtained
Scheme 1. Confirmation the diastereomeric ratio of 2a at low tem-
at –90 °C (Table 2, entries 7 and 9). The replacement of perature.
water with aqueous THF for the hydrolysis clearly did not
improve the dr (Table 2, entries 9 and 10).
The poor dr for hydrolysis of 2a with water–alkali addi-
tives (Table 1, entry 6, Table 2, entry 13) indicated that
simultaneously formed HCl was necessary for the selective
formation of 1a. As shown in Scheme 2, we supposed that
HCl combined with 2a to form quaternary phosphonium
salt 4/4Ј, which was attacked by nucleophilic water, via a
possible five-coordinate phosphorus intermediate 5, to af-
ford 1a/1aЈ. The chloride anion tended to leave from an
axial position of the trigonal bipyramidal 5/5Ј. As seen in
Scheme 2, b, loss of the chloride anion from 5 was less hin-
dered by the bulky ortho-isopropyl group than in 5Ј, which
would result in 1a being formed predominantly.
Table 2. Hydrolysis of menthyl phosphorochloridite 2a.
Entry
Solvent
T [°C]
Ratio of 1a/1aЈ[a]
1
2
3
4
5
6
7
8
9
Pentane
Toluene
Toluene
25
25
–90
25
–80
–80
25
–80
–90
–90
–90
–90
–90
63:37
54:46
68:32
63:37
61:39
71:29
72:28
87:13
89:11 [
CDCl
CDCl
THF
3
3
Et
2
Et
2
Et
2
Et
2
Et
2
Et
2
Et
2
O
O
O
O
More than 1 equiv. of HCl tended to combine with water
+
to form H O and reduce its nucleophilic activity, which
b]
3
10
11
12
13
88:12
would hinder the formation of 5/5Ј. At low temperature
O/pentane
O/HMPA
O/Et
79:21
57:43
66:34 [
(–80 °C), water will be solidified quickly. Due to the limited
b]
3
N
solubility of water in ether, the presence of excess HCl
would lead to incomplete hydrolysis of 2a at low tempera-
ture, and give poor 1a/1aЈ ratio (Table 1, entries 1–3 and 7).
a] The 1a/1aЈ ratio was estimated by 31P NMR spectra. [b] A mix-
[
ture of THF/water was used.
Eur. J. Org. Chem. 2015, 2342–2345
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2343

W.-M. Wang, L.-J. Liu, C.-Q. Zhao, L.-B. Han
Table 3. Conversion of 1a/1aЈ (1:1) to enriched 1a.
SHORT COMMUNICATION
Entry 1/PCl
3
(1a/1aЈ = 50:50)[a] PCl
3
/pyridine[a] 1a/1aЈ [b]
1
2
3
4
5
6
7
8
9
1:1.2
1:0.8
1:0.4
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1
1:1
1:1
1:0
1:1
1:2
1:3
1:0
1:0
88:12
85.5:14.5
79:21
76:24
[
[
[
[
[
c]
c]
c]
d]
e]
86:14
85:15
45:55
54:46
68:32
[
a] Molar ratio. [b] The ratio of 1a/1aЈ was estimated by 31P NMR
spectra. [c] PCl reacted with 1a/1aЈ for 5 h at room temperature.
d] The reaction was carried out in dichloromethane. [e] The reac-
3
[
tion was carried out in THF.
Scheme 2. Proposed mechanism for hydrolysis of 2a.
Conclusions
In summary, P-stereogenic H-phosphinate 1a was pre-
pared directly from commercially available (L)-(–)-menthol.
The presence of 1 equiv. of HCl was necessary for the dia-
stereoselective hydrolysis of the P–Cl species, but excess
HCl resulted in decreased selectivity. The by-produced 1a/
Various chiral alcohols were examined for the prepara-
tion of P-stereogenic phenylphosphinates by a similar pro-
cedure. However, only (L)-(–)-menthol gave satisfactory
selectivity. The corresponding phosphorochloridites 2b, 2c,
and 2d were obtained from borneol, (R)-nonan-2-ol, and
1aЈ mixture can be used for the isolation of 1a by treatment
(S)-ethyl 2-hydroxylpropanoate, respectively. Hydrolysis of
with PCl then hydrolysis at low temperature. Our study
3
2b and 2c in diethyl ether gave 1b and 1c in around 60:40
provided a practical and straightforward method for prepa-
ration of optically pure H–P species that are widely used in
asymmetric catalysis.
dr (Scheme 3). During hydrolysis of 2d, dehydration elimi-
nation occurred and ethyl acrylate was formed as the major
product.
Experimental Section
Typical Procedure to Study the Selectivity for the Formation of 1a:
Phenyl dichlorophosphine (0.52 mL, 3.85 mmol) was added to an
ice-cooled solution of (L)-(–)-menthol (0.5005 g, 3.21 mmol) and
pyridine (0.26 mL, 3.21 mmol) in dry ether (10 mL), under an at-
mosphere of nitrogen. The mixture was stirred at room temperature
for 4.5 h then cooled to –80 °C. Water-saturated diethyl ether
(
20 mL) was added dropwise, and the mixture was stirred at –80 °C
for 4 h. Saturated aqueous NaHCO solution was added to the
mixture and the aqueous layer was extracted with diethyl ether (3ϫ
On the basis of the well-known equilibrium between 20 mL). The combined organic layer was dried with anhydrous
hydrogen phosphinate P(=O)–H and phosphonite P–OH, MgSO . After removing the solvents in vacuo, the residue was ob-
Scheme 3. Hydrolysis of 2 derived from various chiral alcohols.
3
4
1
31
the latter can be converted to P–Cl species by triaryldi- tained as a colorless oil and was analyzed by H and P NMR
1
chlorophosphorus or phosphorus trichloride.[13] We hoped
spectroscopy. H NMR (CDCl , 300 MHz): δ = 7.65 (d, J =
3
3
1
5
52 Hz, 0.16 H), δ = 7.64 (d, J = 552 Hz, 0.84 H) ppm. P NMR
the mixture of 1a/1aЈ could be converted to 2a by phos-
[
14]
(CDCl , 300 MHz): δ = 25.23 (s, 83%), 21.83 (s, 17%) ppm.
3
phorus trichloride, which could afford 1a predominantly
when hydrolyzed at low temperature, as above.
Typical Procedure for the Hydrolysis of 2a: Water (5 μL) was added
to a liquid nitrogen–diethyl ether-cooled solution (–90 °C) of 2a
The conversion of 1a/1aЈ (1:1) to a mixture enriched in
(
50 μL) in diethyl ether (1 mL). The mixture was stirred at the same
1a under different conditions was examined (Table 3). As
temperature for 5 h, then warmed to room temperature and washed
with water three times. After removing the solvent, the residue was
analyzed by NMR spectroscopy. H NMR (CDCl
seen in entries 1 to 3, 1 equiv. of PCl was essential. An
3
inadequate amount of PCl resulted in incomplete conver-
sion of 1a/1aЈ to 2a. The best dr was obtained from a slight
3
1
3
, 300 MHz): δ =
7
.65 (d, J = 552 Hz, 0.11 H), δ = 7.64 (d, J = 552 Hz, 0.89 H) ppm.
P NMR (CDCl , 300 MHz): δ = 25.23 (s, 89%), 21.83 (s, 11%)
3
excess of PCl (1.2 equiv.). It was necessary to remove HCl
31
3
immediately with pyridine (Table 3, entries 4, 8 and 9). Ex-
cellent selectivity was obtained when 1 or 2 equiv. of pyr-
idine was used (Table 3, entries 5–6). In the presence of
ppm.
Preparation of Optically Pure 1a: A solution of (L)-(–)-menthol
(
(
57 g, 0.37 mol) and pyridine (30 mL, 0.37 mol) in dry diethyl ether
250 mL) was added dropwise to an ice-cooled solution of phenyl
3
equiv. of pyridine, the selectivity was completely lost,
since all the HCl was neutralized (Table 3, entry 7), which
dichlorophosphine (50 mL, 0.37 mol) in dry diethyl ether (250 mL),
was similar to the above hydrolysis by water–alkali additive under a nitrogen atmosphere. The mixture was stirred at room tem-
Table 1, entry 6 and Table 2, entry 13). perature for 6 h, and then cooled to –80 °C. At this stage, the reac-
(
2344
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© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 2342–2345

Diastereoselective Hydrolysis of Asymmetric P–Cl Species
tion vessel can be opened to the air. Diethyl ether (500 mL, com-
mercially available without purification) was added, followed by
addition of water (15 mL), the mixture was stirred at –80 °C to
room temperature overnight. Water (500 mL) was added and the
organic layer was washed with water three times (3ϫ 400 mL). Af-
[2] a) N. V. Dubrovina, A. Börner, Angew. Chem. Int. Ed. 2004,
43, 5883; Angew. Chem. 2004, 116, 6007; b) X. Jiang, A. J. Min-
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1503–5886; c) W. M. Dai, K. K. Y. Yeung, W. H. Leung, R. K.
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Minnaard, B. L. Feringa, J. G. de Vries, J. Org. Chem. 2004, 69,
2327–2331.
ter drying over anhydrous MgSO
a colorless oil (100 g, 97% yield) was obtained, with 80:20 dr of 1a/
aЈ. The crude product was recrystallized from pentane (100 mL,
4
and removing solvents in vacuo,
1
commercially available without purification) at –30 °C to afford a
white solid (70 g) in 90:10 dr, which was recrystallized three times
in pentane with a reducing temperature gradient from 20 °C to
–
30 °C to afford optically pure 1a (first crop 15 g, second crop 40 g,
1
and third crop 5 g, in total 60 g, 58% yield) with Ͼ 99:1 dr.
NMR (CDCl , 300 MHz): δ = 7.64 (d, J = 552 Hz, 1 H), 7.74–7.79
m, 2 H), 7.47–7.59 (m, 3 H), 4.22–4.31 (m, 1 H), 2.14–2.22 (m, 2
H), 1.64–1.70 (m, 2 H), 1.41–1.47 (m, 2 H), 1.18–1.27 (q, J = 12 Hz,
H
[
3] a) K. E. DeBruin, C. I. W. Tang, D. M. Johnson, R. L. Wilde,
J. Am. Chem. Soc. 1989, 111, 5871–5879; b) E. E. Nifantyev,
T. S. Kukhareva, D. V. Khodarev, L. K. Vasyanina, Phosphorus
Sulfur Silicon Relat. Elem. 2005, 180, 2733–2743.
3
(
1
7
0
H), 0.98–1.09 (dq, J1 = 3.2 Hz, J2 = 12.8 Hz, 1 H), 0.95 (d, J = [4]
a) Y. Zhou, G. Wang, Y. Saga, R. Shen, M. Goto, Y. Zhao, L.-
B. Han, J. Org. Chem. 2010, 75, 7924–7927; b) G. Wang, R.
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.2 Hz, 3 H), 0.89 (d, J = 6.8 Hz, 3 H), 0.85 (d, J = 6.4 Hz, 3 H),
31
.81–0.91 (m, 1 H) ppm. P NMR (CDCl
3
, 300 MHz): δ = 25.28
s) ppm. 13C NMR (101 MHz, CDCl
(
3
): δ = 133.07, 133.05, 130.86,
2
005, 70, 10121–10123; d) L.-B. Han, C.-Q. Zhao, S.-y. Onoz-
awa, M. Goto, M. Tanaka, J. Am. Chem. Soc. 2002, 124, 3842–
843.
1
4
30.75, 128.92, 128.78, 79.17, 79.10, 77.58, 77.26, 76.95, 48.97,
8.91, 43.72, 34.15, 31.85, 26.01, 23.18, 22.05, 21.17, 15.97 ppm.
3
Typical Procedure for the conversion of 1a/1aЈ to the Product En-
riched in 1a: Phosphorus chloride (38 μL, 0.441 mmol) and pyr-
idine (36.5 μL, 0.441 mmol) were added, in turn, dropwise to a
solution of 1a/1aЈ (102.8 mg, 0.367 mmol, ca. 1:1 dr) in diethyl
ether, under nitrogen. The mixture was stirred at room temperature
for 2 h, and then cooled to –80 °C. Water-saturated ether (5 mL)
was added dropwise and the mixture was stirred at –80 °C for 4 h.
After warming to room temperature, the mixture was washed with
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Z.-Y. Xu, L.-J. Liu, F.-J. Meng, H. Zhang, B.-C. Fu, Q.-J. Li-
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[
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3
water twice and dried with anhydrous MgSO
4
. After removing the
3
solvents in vacuo, the residue was obtained as a colorless oil and
1
31
1
3
was analyzed by H and P NMR spectroscopy. H NMR (CDCl ,
1
3
5
8
00 MHz): δ = 7.65 (d, J = 552 Hz, 0.12 H), δ = 7.64 (d, J =
[9] a) K. Afarinkia, H.-w. Yu, Tetrahedron Lett. 2003, 44, 781–
52 Hz, 0.88 H) ppm. 31P NMR (CDCl
8%), 21.83 (s, 12%) ppm.
3
, 300 MHz): δ = 25.23 (s,
784; b) J. Cai, Z. Zhou, G. Zhao, C. Tang, Heteroat. Chem.
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[
[
[
Acknowledgments
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The authors acknowledge the financial support of the National
Natural Science Foundation of China (grant no. 20772055).
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Published Online: March 5, 2015
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