Systematic study for the stereochemistry of the Atherton-Todd reaction

Article abstract of DOI:10.1016/j.tet.2013.09.001

Under the Atherton-Todd reaction conditions, the stereochemistry on the reaction of H-phosphinates with different nucleophiles (e.g., amines, alcohols, phenols) was investigated. All reactions took place stereospecifically with inversion of configurations at the phosphorus centers. The reaction might proceed via a phosphoryl chloride intermediate with retention of configuration at phosphorus, followed by the attack of nucleophiles from the backside of Cl to give the substitution products with inversion of configuration at the phosphorus center. A plausible mechanism was proposed for these reactions.

Full text of DOI:10.1016/j.tet.2013.09.001

Tetrahedron 69 (2013) 9373e9380
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Systematic study for the stereochemistry of the AthertoneTodd
reaction
Biquan Xiong , Yongbo Zhou , Changqiu Zhao , Midori Goto , Shuang-Feng Yin ,*,
Li-Biao Han
a
a
a
b
c
a
a,c,
*
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082,
PR China
Department of Chemistry, College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000, PR China
b
c
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 June 2013
Received in revised form 24 August 2013
Accepted 2 September 2013
Available online 11 September 2013
Under the AthertoneTodd reaction conditions, the stereochemistry on the reaction of H-phosphinates
with different nucleophiles (e.g., amines, alcohols, phenols) was investigated. All reactions took place
stereospecifically with inversion of configurations at the phosphorus centers. The reaction might proceed
via a phosphoryl chloride intermediate with retention of configuration at phosphorus, followed by the
attack of nucleophiles from the backside of Cl to give the substitution products with inversion of con-
figuration at the phosphorus center. A plausible mechanism was proposed for these reactions.
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
AthertoneTodd reaction
Stereochemistry
H-Phosphinates
Nucleophiles
1. Introduction
the stereochemistry of the AthertoneTodd reaction at phosphorus.
In 1972, Mikolajczyk studied the stereochemistry of the reaction of
Optically active phosphonates and organophosphorus acid de-
optically active phosphoryl halides with alcohols and amines, and
1,2
rivatives are valuable compounds, which not only show biological
found the reaction proceeded with inversion of configuration at the
3
7g
activities related to antitumor, HIV transcriptase inhibition, and
phosphorus center. In 1980, Inch investigated the stereochemis-
immunomodulation,4 but also are important chiral auxiliaries for
try and mechanism of bond forming and breaking at phosphorus in
5
7h
asymmetric catalysis and asymmetric synthesis. It is well known
some five-/six-membered cyclic phosphorus esters. In 2010, we
that P-chirogenic organophosphorus compounds can hardly be
studied the reaction of H-phosphinate with amines under the
AthertoneTodd reaction conditions. On the basis of the X-ray
structure of the product of optically active H-phosphinate with
ammonia, we deduced that this reaction might proceed with
found in the natural product and the synthesis of such compounds
1
a,b,6
in enantiomeric pure forms is usually a hard job.
AthertoneTodd reaction is powerful classical synthetic
a
8
method, which is widely used for the preparation of phosphates
inversion of configuration at the phosphorus center (Scheme 1).
and related phosphorus compounds.7 However, despite extensive
studies, the mechanism of the AthertoneTodd reaction is not fully
understood.7
ceh
Atherton and Todd discovered this reaction in 1945
and proposed a possible mechanism involving a trichloromethyl
7
a
phosphonate intermediate.
AthertoneTodd reaction’s mechanism in 1950, and confirmed the
formation of (RO)
P(O)Cl intermediates in the reaction.7e In 1985,
Engel also proposed a plausible mechanism via a pentacoordinated
Later, Steinberg investigated the
Scheme 1. Previous work: stereospecific coupling of optically active H-phosphinates
2
8
or phosphoryl chlorides with amines.
7
f
phosphoryl chloride intermediate. Moreover, little is known on
To ensure the generality of the conclusion that AthertoneTodd
reaction proceeds stereospecifically with inversion of configuration
at the phosphorus center, the stereochemistry on the reactions of
optically active H-phospinates (1) with other nucleophiles (2)
*
Corresponding authors. Tel./fax: þ86 731 88821171; e-mail addresses: sf_yin@
hnu.edu.cn, yinsf73@163.com (S.-F. Yin), libiao-han@aist.go.jp (L.-B. Han).
0
040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.09.001

9374
B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
(
RNH
2
, ROH, ArOH, ArSH) was studied. Based on the X-ray diffrac-
with inversion of configuration at the phosphorus center in Rp-1a,
8
a
tion analysis, we confirmed that all the reactions took place effi-
ciently with inversion of configurations at the phosphorus centers
which is in consistent with our previous report. We further used
H-phosphinate (Rp-1a, Rp/Sp>99:1) to react with methanol (2b)
under the same reaction conditions, the expected product of Sp-3b
(Scheme 2).
(Sp/Rp>99:1) was obtained in 86% isolated yield. By the compar-
ison of configuration of compound Sp-3b with Rp-2a, the reaction
of H-phosphinates with methanol also took place stereospecifically
with inversion of configuration at the phosphorus center (Table 1,
entry 2, and Fig. 2).
Scheme 2. Outline of the present work.
2
. Results and discussion
In the present study, we first conducted the reaction of Rp-
(
ꢀ)-menthyl phenyl H-phosphinate (Rp-1a, Rp/Sp>99:1) with iso-
butyl amine (2a) under the AthertoneTodd reaction conditions, the
corresponding PeN coupling product Rp-3a (Rp/Sp>99:1) was
generated stereospecifically in 94% yields (Table 1, entry 1). The
stereochemistry of compound Rp-3a was confirmed by X-ray dif-
fraction analysis (Fig. 1). It was shown that this reaction proceeded
Fig. 2. ORTEP drawing of Sp-(ꢀ)-menthyl O-methyl phenylphosphate (Sp-3b). Hy-
drogen atoms are omitted for clarity; ellipsoids are drawn at 50% probability. Selected
ꢀ
ꢁ
bond lengths [A] and angles [ ]: P1eO1 1.571(2), P1eO2 1.458(3), P1eO3 1.575(3),
P1eC11 1.789(4), O1eC3 1.468(5), O3eC17 1.438(5), P1eO1eC3 120.1(2), P1eO3eC17
119.0(3), O2eP1eC11 111.0(2), O2eP1eO3 116.0(2), O2eP1eO1 116.7(2), O3eP1eC11
107.7(2), O1eP1eC11 106.6(2).
Table 1
Stereospecific coupling of optically active H-phosphinates with iso-butyl amine/
methanol under the AthertoneTodd reaction conditions
a
With these results in hand, we further conducted the reaction
of optically active H-phosphinates with phenols under the same
reaction conditions. We first operated the reaction using phenol
(
2c, 1 mmol) as a model substrate, treated with Rp-(ꢀ)-menthyl
phenyl H-phosphinate (Rp-1a, Rp/Sp>99:1, 1 mmol) in CCl (5 mL),
and Et N (2 mmol) was added. The resulting mixture was stirred at
room temperature overnight, then a considerable amount of Rp-
(ꢀ)-menthyl O-phenyl phenylphosphonate (Rp-4a, Rp/Sp>99:1)
was generated in quantitative yield. As shown in Table 2, the
substrates bearing different functional groups, such as alkyl,
alkoxyl, nitro-, and trifluoromethyl could be all efficiently coupled
under this reaction conditions to afford the corresponding opti-
cally active phosphonates with good to excellent isolated yields
4
Entry
1
P*(O)H (1)
Nu-H (2)
Product (3)
Yieldb (%)
94
3
O
O
Ph
P
OMen(-)
N
H
P
H
iso-Butyl amine 2a
Ph
OMen(-)
Rp-1a
Rp-3a
O
OMen(-)
3
H CO P
2
Rp-1a
CH
3
OH 2b
86
Ph
Sp-3b
(
Table 2, entries 2e10). For most cases, electron-donating groups
a
Reaction conditions: nucleophiles (1 mmol) and optically active H-phosphinates
(5 mL), Et N (2 mmol) was added under N at-
(Table 2, entries 5, 9, and 16) or electron-withdrawing groups
(
1 mmol) were dissolved in CCl
4
3
2
mosphere, stirred at room temperature overnight.
(Table 2, entries 6, 7, 10, 13, and 18) on the phenols did not change
the yields of the coupling products significantly. Similarly, the re-
b
Isolated yield.
action of a-/b-naphthol (2m, 2n) or hydroquinone (2p) with Rp-1a
also gave the expected PeO coupling products in 95e97% yields.
Substituted optically active H-phosphinates, such as (ꢀ)-menthyl
phenyl phosphinate (Rp-1a, Rp/Sp>99:1), (ꢀ)-menthyl 2,4,6-
trimethyl-phenyl phosphinate (Rp-1b, Rp/Sp¼97:3), and
(
ꢀ)-menthyl benzyl phosphinate (Rp-1c, Rp/Sp>99:1) could react
efficiently with phenol (2c) to provide the corresponding products
of Rp-4a (Rp/Sp>99:1), Rp-4o (Rp/Sp¼97:3), and Rp-4q
(Rp/Sp>99:1) in 99%, 94%, and 96% yields (Table 1, entries 1, 15, 17),
9
respectively.
It is worth noting that the other diastereomer (Sp) was not
detected from the crude products by employing H NMR and
1
31
P
NMR techniques during the reaction. Moreover, when a di-
astereomeric mixture of 1a (Rp/Sp¼52:48) was employed as the
substrate in the above reaction, 4s was obtained as a mixture of
diastereomers with the same ratio of Rp/Sp¼52:48 (Table 2, entry
Fig. 1. ORTEP drawing of Rp-(ꢀ)-menthyl phenyl N-isobutyl phosphoramidate (Rp-3a).
Hydrogen atoms are omitted for clarity; ellipsoids are drawn at 50% probability. Se-
1
9). Therefore, it is deduced that this reaction proceeds stereo-
ꢀ
ꢁ
lected bond lengths [A] and angles [ ]: P1eO1 1.572(2), P1eO2 1.4722(19), P1eN1
.626(2), P1eC15 1.802(3), C3eO1 1.472(3), C11eN1 1.463(4), P1eO1eC3 124.06(18),
P1eN1eC11 121.4(2), N1eP1eC15 110.92(13), O1eP1eC15 99.64(12), O1eP1eN1
05.33(11), O2eP1eC15 111.60(13), O2eP1eO1 116.63(12), O2eP1eN1 111.96(12).
specifically. In addition, the stereochemistry at phosphorus in Rp-4l
Rp/Sp>99:1) and Rp-4r (Rp/Sp>99:1) was unambiguously de-
termined by X-ray analysis, showing that this reaction proceeded
1
(
1

B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
Table 2 (continued )
9375
Table 2
Stereospecific coupling of optically active H-phosphinates with phenols under the
AthertoneTodd reaction conditions
a
Entry
P*(O)eH (1)
NueH (2)
Product (4)
Yieldb (%)
O
P
O
OMen(-)
16
Rp-1b
2g
96
MeO
Rp-4p
O
O
O
OMen(-)
Bn
H P
P
17
18
2c
2l
96
92
Entry
1
P*(O)eH (1)
NueH (2)
Product (4)
Yieldb (%)
99
OMen(-)
Rp-1c
Bn
Rp-4q
O
O
Ph
O
OMen(-)
H
P
OH
P
O
P
2
O N
O
OMen(-)
Ph
OMen(-)
2c
Rp-1c
Bn
Rp-4a
Rp-1a
Rp-4r
O
P
O
OMen(-)
O
O
2
3
4
5
Rp-1a
Rp-1a
Rp-1a
Rp-1a
OH
98
98
96
98
OMen(-)
P
Ph
Rp-4b
1
2
9
0
Rp-1a, Rp/Sp¼52:48 2c
Rp-1a
92
88
Ph
2
d
Rp-4s, Rp/Sp = 52/48
O
O
OMen(-)
O
t-Bu
n-Bu
MeO
OH
P
SH
S
OMen(-)
P
Ph
2
e
t-Bu
n-Bu
MeO
Ph
Rp-4c
2q
Rp-4t
O
P
O
OMen(-)
Ph
O
P
OH
OH
S
OMen(-)
t-Bu
SH
21
Rp-1c
91
Bn
2
f
Rp-4d
2r
t-Bu
Rp-4u
O
O
OMen(-)
a
P
Reaction conditions: phenol (1 mmol) and optically active H-phosphinate
(1 mmol) were dissolved in CCl4 (5 mL), Et N (2 mmol) was added under N2 at-
Ph
3
2
g
Rp-4e
mosphere, stirred at room temperature overnight.
b
Isolated yield.
O
P
O
OMen(-)
F
3
C
OH
OH
6
7
8
9
Rp-1a
Rp-1a
Rp-1a
Rp-1a
97
99
93
96
Ph
2
h
3
F C
highly stereospecifically with inversion of configuration at the
phosphorus center through the comparison of configuration with
compound Rp-2a (Rp/Sp>99:1) (Figs. 3 and 4). It is noted that this
Rp-4f
O
P
O
OMen(-)
2
O N
8
Ph
conclusion is in consistent with our previous speculation.
2
i
O N
2
OH
O
P
O
OMen(-)
Ph
2
j
Rp-4h
OH
O
P
MeO
O
OMen(-)
Ph
MeO
2
k
Rp-4i
OH
O
P
O
2
N
O
OMen(-)
1
1
0
1
Rp-1a
Rp-1a
96
97
Ph
O
2
N
2
l
Rp-4j
OH
O
O
OMen(-)
P
Ph
Fig. 3. ORTEP drawing of Rp-(ꢀ)-menthyl O-naphthalen-6-yl phenylphosphonate (Rp-
4l). Hydrogen atoms are omitted for clarity; ellipsoids are drawn at 50% probability.
Selected bond lengths [A] and angles [ ]: P1eO1 1.540(3), P1eO2 1.441(4), P1eO3
1.576(4), P1eC11 1.768(6), C2eO3 1.383(6), C21eO1 1.487(5), O1eP1eO2 112.2(2),
P1eO1eC21 128.7(3), C2eO3eP1 129.1(3), O3eP1eC11 105.3(3), O2eP1eO3 116.6(2),
O1eP1eO3 101.67(19), O2eP1eC11 112.6(3), O1eP1eC11 107.5(2).
2
m
Rp-4k
ꢀ
ꢁ
O
P
OH
O
OMen(-)
1
2
Rp-1a
95
Ph
2
n
Rp-4l
O
P
O
OMen(-)
O
F
3
C
OH
1
1
3
4
H P
96
95
Moreover, we conducted the reaction using thiophenols (e.g., 2-
naphthalene-thiol (2q) and 4-tert-butyl thiophenol (2r)) as the
substrates to react with H-phosphinates under the AthertoneTodd
reaction conditions, and the corresponding PeS coupling products
were obtained in 88% (Rp-4t, Rp/Sp>99:1) and 91% (Rp-4u, Rp/
Sp>99:1) isolated yields, respectively (Table 2, entries 20 and 21).
The stereochemistry of compound Rp-4u was unambiguously de-
termined by X-ray diffraction analysis, showing that this reaction
also proceeds with inversion of configuration at the phosphorus
center in Rp-1c (Fig. 5).
F C
OMen(-)
Rp-1b
2o
Rp-4m
Ph
O
P
HO
OH (-)MenO
O
O
Ph
OMen(-)
Rp-1a
Rp-1b
P
O
2p
Rp-4n
O
P
O
OMen(-)
1
5
2c
94
Rp-4o
On the basis of the above results, we also operated the reaction
of optically active phosphoryl chloride Sp-5a (Rp/Sp>99:1) with

9376
B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
Holmes, and Mislow et al.10 Although not fully understood for the
current substitutions, a plausible mechanism is proposed in
Scheme 4. Under the AthertoneTodd reaction condition, the opti-
cally active H-phosphinate is converted to an optical active phos-
8
b,10
phoryl chloride with retention of configuration at phosphorus.
Nucleophiles can attack phosphorus from the backside of Cl to give
the substitution products stereospecifically with inversion of con-
figurations at the phosphorus centers.
Scheme 4. A plausible mechanism for the AthertoneTodd reaction.
Fig. 4. ORTEP drawing of Rp-benzyl (ꢀ)-menthyl O-3-nitrophenylphosphonate (Rp-
r). Hydrogen atoms are omitted for clarity; ellipsoids are drawn at 50% probability.
4
ꢀ
ꢁ
Selected bond lengths [A] and angles [ ]: P1eO1 1.461(3), P1eO2 1.597(3), P1eO3
.561(3), P1eC7 1.790(4), C6eC7 1.506(6), C8eO3 1.477(4), C18eO2 1.398(5), N1eO4
.220(5), N1eO5 1.210(5), N1eC20 1.472(6), O1eP1eO2 113.94(17), O1eP1eO3
14.78(17), O1eP1eC7 118.0(2), O2eP1eO3 105.21(19), O2eP1eC7 97.55(18),
3. Conclusion
1
1
1
In conclusion, we have investigated the stereochemistry of
P1eO3eC8 124.5(3), C6eC7eP1 116.3(3), C7eP1eO3 105.31(18), C18eO2eP1 125.1(3),
O4eN1eO5 123.2(5), O4eN1eC20 118.5(5), O5eN1eC20 118.3(5).
H-phosphinates with different nucleophiles (e.g., amines, alcohols,
phenols) under the AthertoneTodd reaction conditions. Through
the X-ray diffraction analysis for the corresponding products, it is
confirmed that all the reactions proceed stereospecifically with
inversion of configurations at the phosphorus centers. By using this
method, we have successfully prepared a series of optically active
phosphonates or phosphorus acid derivatives via reactions of the
easily available optically active H-phosphinates with nucleophiles
under the mild conditions, which are highly useful materials for the
construction of biologically active molecules, asymmetric catalytic
ligands, and P-chirogenic organophosphorus compounds.
4
4
. Experimental section
.1. General information and materials
All solvents used in reactions were freshly distilled. All other
reagents were recrystallized or distilled as necessary. All reactions
Fig. 5. ORTEP drawing of Rp-(ꢀ)-menthyl S-4-tert-butylphenyl benzyl phosphonothioate
1
were performed under an atmosphere of dry nitrogen.
H
(
Rp-4u). Hydrogen atoms are omitted for clarity; ellipsoids are drawn at 50% probability.
13
31
ꢀ
ꢁ
(400 MHz), C (100 MHz), and P (162 MHz) spectra were recor-
Selected bond lengths [A] and angles [ ]: P1eO1 1.608(9), P1eO2 1.409(9), P1eS1
.103(5), P1eC11 1.766(19), C8eS1 1.778(18), C18eO1 1.488(18), C11eC12 1.50(3),
1
2
ded on a 400 MHz spectrometer in CDCl
are reported using TMS as internal standard; C NMR chemical
shifts are reported relative to CDCl as internal standard. The
3
. H NMR chemical shifts
P1eO1eC18 119.0(9), P1eS1eC8 99.9(7), P1eC11eC12 114.6(14), O1eP1eS1 98.1(4),
O1eP1eC11 105.4(7), S1eP1eC11 106.5(7), O1eP1eP2 113.5(5), S1eP1eO2 114.6(4),
O2eP1eC11 116.8(8).
13
3
electron ionization method was used as the ionization method for
the HRMS measurement, and the mass analyzer type is double-
focusing.
phenol under the nucleophilic substitution reaction conditions,8b
and the expected product was obtained stereospecifically in 91%
1
isolated yield (Rp/Sp>99:1, Scheme 3). By comparison of the H and
31
4.2. Crystallographic information
P NMR data of this product with those of Rp-4a (Rp/Sp>99:1), it
was confirmed that the stereochemistry of the nucleophilic sub-
stitution reaction of phosphoryl chloride with phenol proceeds
stereospecifically with inversion of configuration at the phosphorus
center.
CCDC-921548 (Rp-4r), 921549 (Rp-4l), 921550 (Rp-3a), 921551
Rp-4u), and 799888 (Sp-3b) contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Center via
www.ccdc.cam.ac.uk/data_request/cif.
(
4.3. General procedure
A nucleophile (1 mmol) and an optically active H-phosphinates
Scheme 3. Stereospecific substitution reaction of the optically active phosphoryl
chloride with phenol.
(1 mmol) were dissolved in CCl
4 3
(5 mL), Et N (2 mmol) was added
under N atmosphere, the resulting mixture was stirred at room
2
temperature for 16e24 h. Then the reaction mixture was concen-
trated in vacuo, and the crude was purified by flash column chro-
matography (EtOAc/Hexane¼1:10 to 1:5) to afford the product.
The stereochemistry and mechanism of nucleophilic sub-
stitution reactions at phosphorus were well studied by Debruin,

B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
9377
A typical procedure for the preparation of optically pure H-phos-
phinates (R
)-1a.9 The mixture of
)-(ꢀ)-menthol (100 g,
41 mmol) and pyridine (51.3 mL, 641 mmol) in Et O (200 mL) was
(87.2 mL, 641 mmol) so-
129.6 (d,
J
PeC¼11.4 Hz), 128.6 (d,
J
PeC¼175.4 Hz), 128.4
P
(
L
(d, JPeC¼15.2 Hz), 126.8, 124.6, 120.5 (d, JPeC¼2.9 Hz), 78.7
6
2
(d, JPeC¼7.7 Hz), 48.6 (d, JPeC¼6.7 Hz), 43.1, 34.1, 31.6, 25.7, 22.8,
31
added dropwise with stirring to a PhPCl
2
3
22.0, 21.0, 16.7, 15.4; P NMR (CDCl , 160 MHz): d 14.55. HRMS
ꢁ
lution in Et
2
O (400 mL) at 0 C and then stirred at room tempera-
31 3
calcd for C23H O P: 386.2011, found: 386.2002.
ture overnight. Water (12 mL, 667 mmol) was added, and the
reaction mixture was washed with water and extracted with hex-
ane. The hexane layer was dried over magnesium sulfate, filtered,
4.3.5. (ꢀ)-Menthyl O-4-tert-butylphenyl phenylphosphonate (Rp-
1
4c). Yield: 419.2 mg, Rp/Sp>99:1, (98%). Colorless oil. H NMR
and concentrated. Recrystallization of the mixture in hexane
3
(CDCl , 400 MHz): d 7.85e7.90 (m, 2H), 7.52e7.56 (m, 1H),
ꢁ
(
(
twice) at ꢀ30 C gave pure (R
P
)-1a as a white crystal (R
P
)-1a
7.42e7.48 (m, 2H), 7.26e7.28 (m, 2H), 7.07e7.09 (m, 2H), 4.33e4.41
(m, 1H), 2.16e2.21 (m, 1H), 1.89e1.95 (m, 1H), 1.61e1.65 (m, 2H),
1.33e1.45 (m, 2H), 1.27 (s, 9H), 1.02e1.18 (m, 1H), 0.95e0.99
R
P
/S
P
>99:1).
9
Preparation of H-phosphinates (R
P
)-1b and (R
P
)-1c. PhCH
2
eMgCl
(
(
1.0 M in Et
800 mL) solution of (ꢀ)-MenOPCl
2
O, 800 mL, 800 mmol) was added dropwise to the Et
2
O
(m, 2H), 0.88 (d, J¼6.8 Hz, 3H), 0.82 (d, J¼7.2 Hz, 3H), 0.59 (d,
ꢁ
13
2
(206.4 g, 800 mmol) at 0 C and
J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
148.3 (d, JPeC¼7.6 Hz),
then stirred at room temperature overnight. Recrystallization of the
147.4, 132.4 (d,
(d, JPeC¼191.5 Hz), 128.3 (d, JPeC¼15.3 Hz), 126.3, 120.1 (d,
PeC¼3.8 Hz), 78.7 (d, JPeC¼6.7 Hz), 60.4, 48.5 (d, JPeC¼6.7 Hz), 43.1,
J
PeC¼2.8 Hz), 131.9 (d, JPeC¼9.5 Hz), 128.5
ꢁ
mixture at ꢀ30 C gave pure (R
P
)-1c as white needles (R
P
/S
P
>99:1).
and
(R
P
)-1b was prepared similarly starting from (ꢀ)-MenOPCl
2
J
31
mesitylmagnesium bromide.
34.4, 34.1, 31.6, 31.4, 25.7, 22.9, 22.0, 20.9, 15.4, 14.2; P NMR
CDCl , 160 MHz): 15.31. HRMS calcd for C26 P: 428.2480,
found: 428.2470.
(
3
d
37 3
H O
4
3
.3.1. (ꢀ)-Menthyl phenyl N-iso-butyl phosphoramidate (Rp-
1
a). Yield: 329.7 mg, Rp/Sp>99:1, (94%). White solid. H NMR
(
CDCl
3
, 400 MHz):
d
7.71e7.76 (m, 2H), 7.40e7.44 (m,1H), 7.34e7.38
4.3.6. (ꢀ)-Menthyl O-4-butylphenyl phenylphosphonate (Rp-
1
(
m, 2H), 4.10e4.19 (m, 1H), 2.60e2.63 (m, 3H), 2.26e2.29 (m, 1H),
4d). Yield: 402.5 mg, Rp/Sp>99:1, (96%). Colorless oil. H NMR
1
.91e1.98 (m, 1H), 1.01e1.39 (m, 4H), 0.86 (d, J¼6.4 Hz, 3H),
3
(CDCl , 400 MHz): d 7.83e7.89 (m, 2H), 7.51e7.55 (m, 1H), 7.41e7.46
13
0
.78e0.81 (m, 7H), 0.76 (d, J¼7.2 Hz, 3H), 0.47 (d, J¼6.8 Hz, 3H);
, 100 MHz):
130.7 (d, JPeC¼171.4 Hz), 130.6 (d,
PeC¼9.5 Hz), 130.5 (d, JPeC¼2.9 Hz), 127.2 (d, JPeC¼14.0 Hz), 75.2 (d,
PeC¼6.4 Hz), 47.7 (d, JPeC¼6.6 Hz), 47.4, 42.5, 33.1, 30.5, 28.9 (d,
C
(m, 2H), 7.03e7.08 (m, 4H), 4.36e4.39 (m, 1H), 2.51e2.55 (m, 2H),
2.20e2.23 (m, 1H), 1.90e1.95 (m, 1H), 1.64e1.65 (m, 2H), 1.20e1.63
(m, 7H), 0.95e0.99 (m, 2H), 0.91 (s, 6H), 0.88 (d, J¼7.2 Hz, 3H), 0.81
NMR (CDCl
3
d
J
J
J
1
3
(d, J¼6.8 Hz, 3H), 0.58 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
31
PeC¼6.7 Hz), 24.5, 21.7, 21.1, 20.0, 18.9 (d, JPeC¼1.9 Hz), 14.3;
, 160 MHz): 21.49. HRMS calcd for C20 34NO
51.2327, found: 351.2305.
P
d
148.6 (d, JPeC¼6.6 Hz), 139.2, 132.4 (d, JPeC¼2.8 Hz), 131.9 (d,
PeC¼9.5 Hz), 129.4, 128.4 (d, JPeC¼183 Hz), 128.3 (d, JPeC¼15.2 Hz),
120.4 (d, JPeC¼3.8 Hz), 78.7 (d, JPeC¼6.7 Hz), 48.5 (d, JPeC¼6.7 Hz),
NMR (CDCl
3
3
d
H
2
P:
J
31
4
3.2, 34.9, 34.1, 33.7, 31.6, 25.7, 22.9, 22.3, 22.0, 21.0, 15.4, 14.0;
NMR (CDCl , 160 MHz): 14.74. HRMS calcd for C26
428.2480, found: 428.2467.
P
4
2
4
2
.3.2. (ꢀ)-Menthyl O-methyl phenylphosphate (Sp-3b).8a Yield:
3
d
37 3
H O P:
1
66.5 mg, Sp/Rp>99:1, (86%). White solid. H NMR (CDCl
3
,
00 MHz):
H), 4.13e4.21 (m, 1H), 3.64 (d, J¼11.2 Hz, 3H), 2.23e2.28 (m, 1H),
.77e1.84 (m, 1H), 1.52e1.60 (m, 2H), 1.11e1.41 (m, 3H), 0.86 (d,
J¼6.4 Hz, 3H), 0.75e0.89 (m, 2H), 0.72 (d, J¼7.2 Hz, 3H), 0.43 (d,
d 7.71e7.76 (m, 2H), 7.45e7.47 (m, 1H), 7.38e7.41 (m,
4.3.7. (ꢀ)-Menthyl O-4-methoxy-phenyl phenylphosphonate (Rp-
1
1
4e). Yield: 393.9 mg, Rp/Sp>99:1, (98%). Colorless oil. H NMR
3
(CDCl , 400 MHz): d 7.82e7.87 (m, 2H), 7.51e7.53 (m, 1H), 7.41e7.46
(m, 2H), 7.06e7.08 (m, 2H), 6.74e6.79 (m, 2H), 4.35e4.38 (m, 1H),
3.73 (s, 3H), 2.22e2.25 (m, 1H), 1.91e1.94 (m, 1H), 1.61e1.66 (m,
1
3
J¼7.2 Hz, 3H); C NMR (CDCl
30.7 (d,
PeC¼188.3 Hz), 76.8 (d, JPeC¼6.6 Hz), 51.3 (d, JPeC¼5.3 Hz), 47.4 (d,
3
, 100 MHz):
d
131.2 (d, JPeC¼3.0 Hz),
1
J
PeC¼9.7 Hz), 127.3 (d, PeC¼14.9 Hz), 127.1 (d,
J
J
J
(
2H), 1.34e1.40 (m, 2H), 1.18e1.24 (m, 1H), 0.95e0.99 (m, 2H), 0.89
31
13
PeC¼7.0 Hz), 42.3, 33.0, 30.5, 24.5, 21.7, 21.0, 19.9, 14.2; P NMR
CDCl , 160 MHz): 19.55.
(d, J¼6.4 Hz, 3H), 0.81 (d, J¼6.8 Hz, 3H), 0.57 (d, J¼6.8 Hz, 3H);
C
3
d
NMR (CDCl , 100 MHz):
3
d
156.4, 144.2 (d, JPeC¼7.6 Hz), 132.4
(
d, JPeC¼2.9 Hz), 132.0 (d, JPeC¼9.6 Hz), 128.3 (d, JPeC¼190.6 Hz),
8
a
4
3
4
2
2
.3.3. (ꢀ)-Menthyl O-phenyl phenylphosphonate (Rp-4a). Yield:
128.3 (d, JPeC¼15.2 Hz), 121.6 (d, JPeC¼3.8 Hz), 114.5, 78.8
1
68.2 mg, Rp/Sp>99:1, (99%). Colorless oil. H NMR (CDCl
3
,
(d, JPeC¼7.6 Hz), 55.6, 48.5 (d, JPeC¼6.7 Hz), 43.2, 34.1, 31.6, 25.7,
31
00 MHz): 7.83e7.89 (m, 2H), 7.51e7.55 (m, 1H), 7.41e7.46 (m,
d
3
22.9, 22.0, 21.0, 15.4; P NMR (CDCl , 160 MHz): d 15.04. HRMS
H), 7.23e7.27 (m, 2H), 7.15e7.17 (dd, JHeH¼1.2 Hz, JPeH¼6.4 Hz,
31 4
calcd for C23H O P: 402.1960, found: 402.1956.
H), 7.07e7.11 (m, 1H), 4.37e4.40 (m, 1H), 2.16e2.25 (m, 1H),
1
.91e1.95 (m, 1H), 1.45e1.65 (m, 2H), 1.34e1.44 (m, 2H), 1.16e1.24
4.3.8. (ꢀ)-Menthyl O-4-trifluoromethyl-phenyl phenylphosphonate
1
(
3
m, 1H), 0.95e0.99 (m, 2H), 0.89 (d, J¼6.4 Hz, 3H), 0.82 (d, J¼6.8 Hz,
(Rp-4f). Yield: 426.6 mg, Rp/Sp>99:1, (97%). Yellow oil. H NMR
13
H), 0.58 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
150.7 (d,
3
(CDCl , 400 MHz): d 7.83e7.89 (m, 2H), 7.44e7.58 (m, 5H),
7.28e7.30 (m, 2H), 4.37e4.45 (m, 1H), 2.21e2.24 (m, 1H), 1.89e1.95
(m, 1H), 1.63e1.67 (m, 2H), 1.35e1.47 (m, 2H), 1.18e1.26 (m, 1H),
J
1
J
3
PeC¼7.6 Hz), 132.5 (d, JPeC¼2.8 Hz), 131.9 (d, JPeC¼10.5 Hz), 129.5,
28.4 (d, JPeC¼15.3 Hz), 128.3 (d, JPeC¼191.6 Hz), 124.6, 120.7 (d,
PeC¼4.7 Hz), 78.8 (d, JPeC¼7.6 Hz), 48.5 (d, JPeC¼7.6 Hz), 43.2, 34.1,
0.97e1.03 (m, 2H), 0.89 (d, J¼6.4 Hz, 3H), 0.82 (d, J¼6.8 Hz, 3H),
31
13
1.6, 25.7, 22.9, 22.0, 20.9, 15.4; P NMR (CDCl
3
, 160 MHz):
d
14.69.
0.59 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz): d 153.3 (d,
J
PeC¼6.7 Hz), 132.8 (d, JPeC¼2.9 Hz), 131.9 (d, JPeC¼10.5 Hz), 128.5
(d, JPeC¼12.4 Hz), 127.0 (d, JPeC¼5.7 Hz), 126.9 (d, JPeC¼2.9 Hz),
126.7 (d, JPeC¼6.7 Hz), 123.9 (d, PeC¼269.7 Hz), 120.9 (d,
PeC¼4.7 Hz), 79.3 (d, JPeC¼6.6 Hz), 48.5 (d, JPeC¼6.7 Hz), 43.2, 34.0,
4
.3.4. (ꢀ)-Menthyl O-o-tolyl phenylphosphonate (Rp-4b). Yield:
1
378.3 mg, Rp/Sp>99:1, (98%). Colorless oil. H NMR (CDCl
400 MHz): 7.86e7.92 (m, 2H), 7.52e7.56 (m, 1H), 7.43e7.47 (m,
2H), 7.26e7.29 (m, 1H), 7.10e7.15 (m, 1H), 7.03e7.09 (m, 1H), 7.01 (t,
3
,
J
d
J
31
31.6, 25.7, 22.8, 22.0, 20.9, 15.4; P NMR (CDCl
3
, 160 MHz): d 15.04.
J¼7.2 Hz), 4.35e4.38 (m, 1H), 2.26 (s, 3H), 2.13e2.17 (m, 1H),
HRMS calcd for C23 P: 440.1728, found: 440.1726.
28 3 3
H F O
1
.89e1.93 (m, 1H), 1.60e1.64 (m, 2H), 1.32e1.39 (m, 2H), 1.08e1.17
(
3
m, 1H), 0.95e0.98 (m, 2H), 0.86 (d, J¼6.4 Hz, 3H), 0.81 (d, J¼6.8 Hz,
4.3.9. (ꢀ)-Menthyl O-4-nitrophenyl phenylphosphonate (Rp-
1
13
H), 0.58 (d, J¼7.2 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
149.3 (d,
4g). Yield: 412.7 mg, Rp/Sp>99:1, (99%). Yellow oil. H NMR (CDCl
3
,
J
PeC¼7.6 Hz), 132.4 (d, JPeC¼2.9 Hz), 131.8 (d, JPeC¼10.5 Hz), 131.2,
400 MHz): 8.15e8.19 (m, 2H), 7.83e7.88 (m, 2H), 7.56e7.60
d

9378
B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
(
2
m, 1H), 7.45e7.50 (m, 2H), 7.32e7.35 (m, 2H), 4.40e4.46 (m, 1H),
.25e2.29 (m, 1H), 1.90e1.94 (m, 1H), 1.64e1.68 (m, 2H), 1.43e1.59
(d, JPeC¼6.9 Hz), 43.0, 33.8, 31.4, 25.6, 22.7, 21.8, 20.8, 15.2; 31P NMR
(CDCl
3 31 3
, 160 MHz): d 16.08. HRMS calcd for C26H O P: 422.2011,
(
0
1
1
m, 2H),1.22e1.31 (m,1H), 0.95e1.01 (m, 2H), 0.92 (d, J¼6.4 Hz, 3H),
found: 422.2003.
13
.83 (d, J¼7.6 Hz, 3H), 0.59 (d, J¼6.8 Hz, 3H); C NMR (CDCl
155.7 (d, JPeC¼6.7 Hz), 144.4, 133.1 (d, JPeC¼2.9 Hz),
PeC¼10.5 Hz), 128.7 (d, PeC¼15.3 Hz), 127.2 (d,
3
,
00 MHz):
d
4.3.14. (ꢀ)-Menthyl O-naphthalen-6-yl phenylphosphonate (Rp-
4l). Yield: 400.6 mg, Rp/Sp>99:1, (94%). White solid. 1H NMR
(CDCl , 400 MHz): d 7.88e7.93 (m, 2H), 7.72e7.74 (m, 3H), 7.66 (s,
3
1H), 7.46e7.54 (m, 1H), 7.37e7.46 (m, 4H), 7.31e7.34 (m, 1H),
4.41e4.46 (m, 1H), 2.20e2.31 (m, 1H), 1.94e1.98 (m, 1H), 1.61e1.66
(m, 2H), 1.36e1.46 (m, 2H), 1.19e1.28 (m, 1H), 0.88e1.01 (m, 2H),
31.9 (d,
J
J
J
4
PeC¼191.6 Hz), 125.5, 121.1 (d, JPeC¼4.7 Hz), 79.6 (d, JPeC¼7.7 Hz),
3
1
8.5 (d, JPeC¼6.7 Hz), 43.2, 34.0, 31.7, 25.8, 22.9, 22.0, 20.9, 15.4;
P
NMR (CDCl
4
3
, 160 MHz): 15.22. HRMS calcd for C22 28NO P:
d
H
5
17.1705, found: 417.1698.
0
.86 (d, J¼7.6 Hz, 3H), 0.83 (d, J¼7.2 Hz, 3H), 0.61 (d, J¼7.2 Hz, 3H);
13
4
3
4
2
.3.10. (ꢀ)-Menthyl O-m-tolyl phenylphosphonate (Rp-4h). Yield:
C NMR (CDCl
131.9 (d, JPeC¼9.9 Hz), 130.7, 129.5, 128.3 (d, JPeC¼15.3 Hz), 128.1 (d,
PeC¼190.7 Hz), 127.6, 127.4, 126.4, 125.2, 120.7 (d, JPeC¼4.6 Hz),
117.0 (d, JPeC¼4.6 Hz), 78.9 (d, JPeC¼6.9 Hz), 48.4 (d, JPeC¼6.8 Hz),
3
, 100 MHz):
d
148.3 (d, JPeC¼6.8 Hz), 133.8, 132.5,
1
58.9 mg, Rp/Sp>99:1, (93%). Colorless oil. H NMR (CDCl
00 MHz): 7.85e7.90 (m, 2H), 7.51e7.55 (m, 1H), 7.41e7.46 (m,
H), 7.12 (t, J¼7.6 Hz, 1H), 7.02 (s, 1H), 6.95 (d, J¼8.4 Hz, 1H), 6.90 (d,
3
,
d
J
31
J¼7.2 Hz, 1H), 4.35e4.42 (m, 1H), 2.28 (s, 3H), 2.23e2.27 (m, 1H),
3
43.1, 34.0, 31.5, 25.6, 22.8, 21.9, 20.89, 15.3; P NMR (CDCl ,
1.89e1.95 (m, 1H), 1.61e1.67 (m, 2H), 1.34e1.47 (m, 2H), 1.16e1.26
160 MHz):
422.2002.
31 3
d 15.95. HRMS calcd for C26H O P: 422.2011, found:
(
3
m, 1H), 0.92e0.99 (m, 2H), 0.89 (d, J¼6.4 Hz, 3H), 0.81 (d, J¼7.2 Hz,
13
H), 0.59 (d, J¼7.2 Hz, 3H); C NMR (CDCl
3
, 100 MHz): d 150.5 (d,
J
1
(
PeC¼6.9 Hz), 139.6, 132.3 (d, JPeC¼3 Hz), 131.8 (d, JPeC¼9.9 Hz),
29.1, 128.3 (d, JPeC¼190.7 Hz), 128.2 (d, JPeC¼15.2 Hz), 125.3, 121.2
d, JPeC¼3.1 Hz),117.4 (d, JPeC¼4.6 Hz), 78.6 (d, JPeC¼6.9 Hz), 48.4 (d,
4.3.15. (ꢀ)-Menthyl O-4-(trifluoromethyl)phenyl 2,4,6-
trimethylphenylphosphonate (Rp-4m). Yield: 462.5 mg, Rp/
1
Sp¼97:3, (96%). Yellow oil. H NMR (CDCl
3
, 400 MHz): d 7.51 (d,
31
J
PeC¼6.8 Hz), 43.1, 34.0, 31.5, 25.6, 22.7, 21.9, 21.2, 20.8, 15.3;
P
J¼8.4 Hz, 2H), 7.25 (s, 2H), 7.23 (s, 2H), 4.49e4.58 (m, 1H), 2.65 (d,
J¼1.2 Hz, 1H), 2.29 (s, 3H), 2.19e2.23 (m, 1H), 1.81e1.89 (m, 1H),
1.63e1.68 (m, 2H), 1.44e1.49 (m, 2H), 1.19e1.38 (m, 1H), 0.91e1.01
3 31 3
NMR (CDCl , 160 MHz): d 15.68. HRMS calcd for C23H O P:
3
86.2011, found: 386.2005.
(
m, 2H), 0.91 (d, J¼6.8 Hz, 3H), 0.81 (d, J¼6.8 Hz, 3H), 0.68 (d,
13
4
4
4
2
4
1
0
0
.3.11. (ꢀ)-Menthyl O-3-methoxyphenyl phenylphosphonate (Rp-
J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
153.5 (d, JPeC¼6.7 Hz),
1
i). Yield: 385.7 mg, Rp/Sp>99:1, (96%). Yellow oil. H NMR (CDCl
3
,
143.6 (d,
J
PeC¼12.4 Hz), 142.4 (d,
J
PeC¼2.9 Hz), 130.5 (d,
00 MHz): 7.85e7.90 (m, 2H), 7.51e7.53 (m, 1H), 7.41e7.46 (m,
d
J
PeC¼16.2 Hz), 126.9 (d, JPeC¼3.8 Hz), 126.5 (d, JPeC¼32.4 Hz), 121.6
H), 7.13 (t, J¼8 Hz, 1H), 6.75e6.78 (m, 2H), 6.63e6.66 (m, 1H),
.37e4.43 (m, 1H), 3.72 (s, 3H), 2.25e2.31 (m, 1H), 1.91e1.95 (m,
H), 1.61e1.66 (m, 2H), 1.34e1.47 (m, 2H), 1.18e1.27 (m, 1H),
.93e1.00 (m, 2H), 0.89 (d, J¼6.8 Hz, 3H), 0.81 (d, J¼6.8 Hz, 3H),
(d, JPeC¼195.4 Hz), 120.6 (d, JPeC¼5.7 Hz), 78.5 (d, JPeC¼7.6 Hz), 48.6
(d, JPeC¼6.6 Hz), 43.2, 34.1, 31.7, 25.9, 23.4, 23.3, 23.0, 22.1, 21.2,
31
3
20.9, 15.5; P NMR (CDCl , 160 MHz): d 16.96. HRMS calcd for
26 34 3 3
C H F O P: 482.2198, found: 482.2207.
13
.58 (d, J¼7.2 Hz, 3H); C NMR (CDCl
3
, 100 MHz): d 160.4, 151.5 (d,
J
1
PeC¼6.9 Hz), 132.4 (d, JPeC¼3 Hz), 131.8 (d, JPeC¼10.0 Hz), 129.7,
28.2 (d, JPeC¼15.3 Hz), 128.1 (d, JPeC¼190.7 Hz), 112.7 (d,
PeC¼3.8 Hz), 110.6, 106.5, 78.7 (d, PeC¼6.9 Hz), 55.2 (d,
4.3.16. Di-(ꢀ)-menthyl O-diphenyl 1,4-phenylene diphosphonate
1
(Rp-4n). Yield: 632.6 mg, Rp/Sp>99:1, (95%). Colorless oil. H NMR
J
J
2
C
J
3
(CDCl , 400 MHz): d 7.77e7.83 (m, 4H), 7.49e7.54 (m, 2H),
PeC¼2.3 Hz), 48.4 (d, JPeC¼6.8 Hz), 43.1, 33.9, 31.5, 25.6, 22.7, 21.9,
7.39e7.44 (m, 4H), 7.05 (s, 4H), 4.31e4.39 (m, 2H), 2.21e2.24 (m,
2H), 1.87e1.93 (m, 2H), 1.62e1.64 (m, 4H), 1.32e1.44 (m, 4H),
1.14e1.23 (m, 2H), 0.94e1.01 (m, 4H), 0.88 (d, J¼6.4 Hz, 1H), 0.80 (d,
0.8, 15.3; 31P NMR (CDCl
P: 402.1960, found: 402.1949.
3
, 160 MHz): d 15.65. HRMS calcd for
23 31 4
H O
13
J¼7.2 Hz, 2H), 0.56 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
4
4
.3.12. (ꢀ)-Menthyl O-3-nitrophenyl phenylphosphonate (Rp-
d
147.2 (d, JPeC¼6.6 Hz), 132.5 (d, JPeC¼3.8 Hz), 131.9, 131.8, 128.4 (d,
PeC¼15.2 Hz), 128.0 (d, JPeC¼190.7 Hz), 121.5 (d, JPeC¼4.8 Hz), 78.9
(d, JPeC¼6.7 Hz), 48.5 (d, JPeC¼7.7 Hz), 43.2, 34.0, 31.6, 25.7, 22.8,
1
j). Yield: 400.1 mg, Rp/Sp>99:1, (96%). Yellow solid. H NMR
J
(
7
(
1
CDCl
.57e7.61 (m, 2H), 7.44e7.51 (m, 3H), 4.40e4.46 (m, 1H), 2.24e2.28
m, 1H), 1.90e1.94 (m, 1H), 1.64e1.70 (m, 2H), 1.38e1.49 (m, 2H),
.21e1.30 (m, 1H), 0.94e1.01 (m, 2H), 0.91 (d, J¼6.0 Hz, 3H), 0.83 (d,
3
, 400 MHz): d 7.98e8.03 (m, 2H), 7.85e7.91 (m, 2H),
31
22.0, 20.9, 15.4; P NMR (CDCl
3
, 160 MHz): d 14.85. HRMS calcd for
38 52 6 2
C H O P : 666.3239, found: 666.3236.
13
J¼6.8 Hz, 3H), 0.59 (d, J¼6.8 Hz, 3H); C NMR (CDCl
151.1 (d, JPeC¼6.9 Hz), 148.8, 133.0, 131.8 (d, JPeC¼10.7 Hz), 130.1,
28.6 (d, JPeC¼16.0 Hz), 127.2 (d, JPeC¼191.5 Hz), 127.0 (d,
3
, 100 MHz):
4.3.17. (ꢀ)-Menthyl O-phenyl 2,4,6-trimethylphenylphosphonate
1
d
(Rp-4o). Yield: 389.1 mg, Rp/Sp¼97:3, (94%). Colorless oil. H NMR
1
3
(CDCl , 400 MHz): d 7.22e7.24 (m, 2H), 7.05e7.14 (m, 3H), 6.89 (d,
J
4
PeC¼3.8 Hz), 119.6, 116.2 (d, JPeC¼5.4 Hz), 79.5 (d, JPeC¼6.8 Hz),
J¼4.8 Hz, 2H), 4.48e4.52 (m, 1H), 2.65 (d, J¼1.6 Hz, 1H), 2.28 (s, 3H),
2.19e2.25 (m, 1H), 1.77e1.88 (m, 1H), 1.61e1.67 (m, 2H), 1.40e1.51
(m, 2H), 1.16e1.36 (m, 1H), 0.97e1.05 (m, 2H), 1.04 (d, J¼10.0 Hz,
3
1
8.4 (d, JPeC¼6.9 Hz), 43.2, 33.9, 31.6, 25.7, 22.8, 21.9, 20.8, 15.3;
P
NMR (CDCl
3
, 160 MHz): 16.57. HRMS calcd for C22 28NO P:
d
H
5
13
417.1705, found: 417.1681.
3H), 0.80 (d, J¼7.2 Hz, 3H), 0.67 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
,
1
00 MHz):
d
150.9 (d, JPeC¼6.6 Hz), 143.6 (d, JPeC¼12.4 Hz), 142.0 (d,
4
4
.3.13. (ꢀ)-Menthyl O-naphthalen-5-yl phenylphosphonate (Rp-
JPeC¼2.9 Hz), 130.4 (d, JPeC¼16.2 Hz), 129.4, 124.3, 122.3 (d,
JPeC¼184.9 Hz), 120.4 (d, JPeC¼4.7 Hz), 78.0 (d, JPeC¼7.6 Hz), 48.6 (d,
JPeC¼6.7 Hz), 43.2, 34.1, 31.7, 25.8, 23.4 (d, JPeC¼1.9 Hz), 23.0, 22.1,
1
k). Yield: 408.9 mg, Rp/Sp>99:1, (97%). Colorless oil. H NMR
(
(
7
(
CDCl
m, 1H), 7.48e7.58 (m, 2H), 7.44e7.46 (m, 3H), 7.38e7.43 (m, 2H),
.30e7.34 (m, 1H), 4.41e4.50 (m, 1H), 2.18e2.24 (m, 1H), 1.92e2.01
m, 1H), 1.58e1.64 (m, 2H), 1.33e1.43 (m, 2H), 1.10e1.18 (m, 1H),
.86e1.01 (m, 2H), 0.82 (s, 3H), 0.81 (s, 3H), 0.61 (d, J¼7.2 Hz, 3H);
3
, 400 MHz): d 8.16e8.18 (m,1H), 7.92e7.98 (m, 2H), 7.76e7.78
3
1
21.2, 21.0, 15.5; P NMR (CDCl
3
, 160 MHz):
d 16.56. HRMS calcd for
25 35 3
C H O P: 414.2324, found: 414.2312.
0
4 . 3 . 18 . ( ꢀ) - M e n t h y l O - 4 - m e t h o x y - p h e n y l 2 , 4 , 6 -
1
3
C NMR (CDCl
3
, 100 MHz):
d
146.5 (d, JPeC¼7.7 Hz), 134.6, 132.4 (d,
trimethylphenylphosphonate (Rp-4p). Yield: 426.2 mg, Rp/
1
J
PeC¼3.1 Hz),131.7 (d, JPeC¼9.9 Hz),128.3 (d, JPeC¼15.3 Hz),128.1 (d,
Sp¼97:3, (96%). Colorless oil.
3
H NMR (CDCl , 400 MHz):
JPeC¼191.5 Hz), 127.5, 126.5 (d, JPeC¼6.1 Hz), 126.3, 125.9, 125.4,
d
7.03e7.05 (m, 2H), 6.77 (d, J¼3.6 Hz, 2H), 6.73e6.76 (m, 2H),
1
24.3, 121.8, 115.3 (d, JPeC¼3.8 Hz), 78.8 (d, JPeC¼6.9 Hz), 48.3
4.48e4.51 (m, 1H), 3.73 (s, 3H), 2.64 (d, J¼1.2 Hz, 6H), 2.28 (s, 3H),

B. Xiong et al. / Tetrahedron 69 (2013) 9373e9380
9379
2
.18e2.21 (m, 1H), 1.82e1.86 (m, 1H), 1.61e1.67 (m, 2H), 1.35e1.47
(d, JPeC¼8.2 Hz), 47.5 (d, JPeC¼5.9 Hz), 42.2, 32.9, 30.6, 24.5, 21.7,
31
(
m, 2H),1.15e1.32 (m,1H), 0.99e1.02 (m, 2H), 0.90 (d, J¼6.4 Hz, 3H),
20.9, 19.9, 14.3; P NMR (CDCl
3
, 160 MHz): d 40.05. HRMS calcd for
13
0
.81 (d, J¼6 Hz, 3H), 0.66 (d, J¼6.8 Hz, 3H); C NMR (CDCl
156.2, 144.4 (d, JPeC¼7.6 Hz), 143.6 (d, JPeC¼12.3 Hz),
PeC¼2.8 Hz), 130.3 (d, PeC¼16.2 Hz), 122.3 (d,
PeC¼184.9 Hz), 121.3 (d, JPeC¼4.8 Hz), 114.4, 78.0 (d, JPeC¼7.6 Hz),
5.6, 48.6 (d, JPeC¼6.7 Hz), 43.2, 34.2, 31.7, 25.8, 23.4 (d,
3
,
26 31 2
C H O
PS: 438.1782, found: 438.1770.
1
1
J
5
00 MHz):
41.9 (d,
d
J
J
4.3.23. (ꢀ)-Menthyl S-4-tert-butylphenyl benzyl phosphonothioate
1
(Rp-4u). Yield: 416.8 mg, Rp/Sp>99:1, (91%). White solid. H NMR
(CDCl
3
, 400 MHz):
d
7.39e7.42 (m, 2H), 7.27 (d, J¼8.4 Hz, 2H),
31
J
PeC¼2.9 Hz), 23.0, 22.1, 21.2, 21.0, 15.5; P NMR (CDCl
3
, 160 MHz):
7.16e7.18 (m, 5H), 4.27e4.36 (m, 1H), 3.16e3.30 (m, 2H), 2.20e2.24
(m,1H),1.13e1.57 (m, 3H),1.24 (s, 9H),1.02e1.20 (m, 3H), 0.70e0.93
d
16.98. HRMS calcd for C26H O P: 444.2429, found: 444.2424.
37 4
(
m, 2H), 0.83 (d, J¼6.8 Hz, 3H), 0.63 (d, J¼7.2 Hz, 3H), 0.48 (d,
13
4
.3.19. (ꢀ)-Menthyl O-phenyl benzylphosphonate (Rp-4q). Yield:
J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz):
d
150.9 (d, JPeC¼2.4 Hz),
1
3
4
1
1
(
70.3 mg, Rp/Sp>99:1, (96%). Colorless oil. H NMR (CDCl
00 MHz): 7.23e7.33 (m, 7H), 7.10e7.14 (m, 3H), 4.30e4.35 (m,
H), 3.21e3.36 (m, 2H), 1.92e1.96 (m, 1H), 1.78e1.83 (m, 1H),
.58e1.62 (m, 2H), 1.26e1.37 (m, 2H), 1.01e1.06 (m, 1H), 0.98e1.01
m, 2H), 0.83 (d, J¼7.2 Hz, 3H), 0.81 (d, J¼6.4 Hz, 3H), 0.63 (d,
3
,
133.5 (d, JPeC¼4.2 Hz), 129.9 (d, JPeC¼9.9 Hz), 129.2 (d, JPeC¼6.8 Hz),
127.2 (d, JPeC¼3.2 Hz), 125.9 (d, JPeC¼2.9 Hz), 125.4 (d, JPeC¼1.6 Hz),
122.9 (d, JPeC¼5.1 Hz), 76.9 (d, JPeC¼8.6 Hz), 47.6 (d, JPeC¼5.6 Hz),
41.9, 39.2 (d, JPeC¼100.7 Hz), 33.6, 32.9, 30.5, 30.2, 23.9, 21.5, 21.1,
d
3
1
20.0, 14.1; P NMR (CDCl
3
, 160 MHz): d 46.86. HRMS calcd for
13
J¼7.2 Hz, 3H); C NMR (CDCl
31.2 (d, JPeC¼8.6 Hz), 130.0 (d, JPeC¼6.7 Hz), 129.6, 128.5 (d,
PeC¼2.9 Hz), 126.9 (d, JPeC¼3.8 Hz), 124.7, 120.6 (d, JPeC¼4.7 Hz),
8.5 (d, JPeC¼8.6 Hz), 48.5 (d, JPeC¼7.7 Hz), 43.1, 34.0, 33.9 (d,
3
, 100 MHz):
d
150.8 (d, JPeC¼8.5 Hz),
27 39 2
C H O PS: 458.2408, found: 458.2397.
1
J
7
Acknowledgements
31
J
PeC¼139.2 Hz), 31.5, 25.4, 22.7, 21.9, 21.0, 15.4; P NMR (CDCl
3
,
This work was supported by the program for New Century Ex-
cellent Talents in Universities (NCET-10e0371), the NSF of Hunan
Province (10JJ1003), the NSFC (21273066, 21273067), Program for
Changjiang Scholars and Innovative Research Team in University
(IRT1238), the Fundamental Research Funds for the Central Uni-
versities, and the Canon Foundation. B.X. and Dr. Y.Z. contributed
equally to this work.
160 MHz): 22.41. HRMS calcd for C23 P: 386.2011, found:
d
31 3
H O
3
86.2005.
4
4
.3.20. (ꢀ)-Menthyl O-3-nitro-phenyl benzylphosphonate (Rp-
1
r). Yield: 418.1 mg, Rp/Sp>99:1, (97%). White solid. H NMR
(
CDCl
3
, 400 MHz): d 7.95e7.98 (m, 1H), 7.86 (s, 1H), 7.42 (d,
J¼5.6 Hz, 2H), 7.25e7.33 (m, 3H), 4.33e4.41 (m, 1H), 3.34 (d,
J
PeH¼21.6 Hz, 2H), 1.95e1.98 (m, 1H), 1.83e1.89 (m, 1H), 1.62e1.66
Supplementary data
(
3
1
1
m, 2H), 1.30e1.42 (m, 2H), 0.93e1.26 (m, 3H), 0.86 (d, J¼7.2 Hz,
13
H), 0.83 (d, J¼6.8 Hz, 3H), 0.69 (d, J¼6.8 Hz, 3H); C NMR (CDCl
151.4 (d, JPeC¼8.0 Hz), 148.8, 130.4 (d, JPeC¼9.6 Hz),
30.0 (d, JPeC¼4.8 Hz), 129.9, 128.7 (d, JPeC¼2.9 Hz), 127.3 (d,
3
,
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2013.09.001.
These data include MOL files and InChiKeys of the most important
compounds described in this article.
00 MHz): d
J
PeC¼4.0 Hz), 126.8 (d, JPeC¼3.8 Hz), 119.4, 116.0 (d, JPeC¼4.7 Hz),
7
3
d
9.1 (d, JPeC¼8.2 Hz), 48.5 (d, JPeC¼6.4 Hz), 34.2 (d, JPeC¼138.0 Hz),
31
3.9, 31.5, 25.6, 22.8, 21.9, 20.9, 15.5; P NMR (CDCl
3
, 160 MHz):
References and notes
5
23.16. HRMS calcd for C23H30NO P: 431.1862, found: 431.1844.
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8
Marcel Dekker: New York, NY, 1992; Chapter 1, pp 5e8; (b) Quin, L. D. A Guide to
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4
3
4
2
4
.3.21. (ꢀ)-Menthyl O-phenyl phenylphosphonate (Rp-4s). Yield:
1
42.1 mg, Rp/Sp¼52:48, (92%). Colorless oil. H NMR (CDCl
3
,
00 MHz): 7.85e7.90 (m, 2H), 7.50e7.54 (m, 1H), 7.42e7.45 (m,
d
2
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m, 2H), 1.22e1.39 (m, 2H), 1.14e1.19 (m, 1H), 0.95e0.99 (m, 2H),
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(
0
13
.84e0.90 (m, 3H), 0.78e0.83 (m, 4.5H), 0.59 (d, J¼6.8 Hz,1.5H);
, 100 MHz):
149.9 (d, JPeC¼7.0 Hz), 149.7 (d,
PeC¼7.0 Hz), 131.5 (d, JPeC¼2.9 Hz), 131.4 (d, JPeC¼1.9 Hz), 130.9 (d,
PeC¼4.6 Hz), 130.8 (d, JPeC¼4.7 Hz), 128.5, 128.1 (d, JPeC¼190.9 Hz),
27.4 (d, PeC¼191.1 Hz), 127.2
PeC¼4.8 Hz), 127.3 (d,
C
3
NMR (CDCl
J
J
1
(
J
J
2
3
d
J
J
129, 11892.
d, JPeC¼4.9 Hz), 123.6, 123.5, 119.7 (d, JPeC¼4.5 Hz), 119.5 (d,
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PeC¼4.5 Hz), 78.1 (d, JPeC¼7.2 Hz), 77.8 (d, JPeC¼7.0 Hz), 47.6 (d,
PeC¼6.4 Hz), 47.5 (d, JPeC¼7.0 Hz), 42.1, 42.0, 33.0, 30.6, 30.5, 24.7,
31
3
4.5, 21.9, 20.9, 20.8, 22.0, 19.9, 14.6, 14.4; P NMR (CDCl ,
160 MHz):
d
14.56,
d
13.91.
5
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4
.3.22. (ꢀ)-Menthyl S-naphthalen-6-yl phenylphosphonothioate
1
(
(
6
Rp-4t). Yield: 385.5 mg, Rp/Sp>99:1, (88%). Yellow oil. H NMR
CDCl , 400 MHz): 7.79 (s, 1H), 7.57e7.68 (m, 5H), 7.23e7.9 (m,
H), 4.39e4.48 (m, 1H), 2.24e2.27 (m, 1H), 1.82e1.90 (m, 1H), 1.57
3
d
(
d, J¼12.0 Hz, 2H), 1.28e1.40 (m, 2H), 1.12e1.21 (m, 1H), 0.82e0.93
1
23, 9908.
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(
m, 1H), 0.81 (d, J¼6.8 Hz, 3H), 0.75e0.80 (m, 1H), 0.73 (d, J¼7.2 Hz,
6
13
3
H), 0.56 (d, J¼6.8 Hz, 3H); C NMR (CDCl
3
, 100 MHz): d 134.2 (d,
2
J
J
(
PeC¼5.6 Hz), 132.4 (d, JPeC¼2.2 Hz), 131.8 (d, JPeC¼1.7 Hz), 131.2 (d,
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d, JPeC¼10.6 Hz), 127.5 (d, JPeC¼1.4 Hz), 127.1 (d, JPeC¼14.8 Hz),
7
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1
26.7, 126.5, 125.8, 125.4, 123.1 (d,
JPeC¼5.4 Hz), 78.0

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(
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2
8
2
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. Optically pure HeP(O) compounds can be purchased from Katayama Chemical
Industries Ltd. (http://www.katayamaka-gaku.co.jp). For their preparation, see:
9
(
a) Farnham, W. B.; Murray, R. K.; Mislow, K. J. Am. Chem. Soc. 1970, 92, 5808; (b)
Reiff, L. P.; Aaron, H. S. J. Am. Chem. Soc. 1970, 92, 5275; (c) Xu, Q.; Zhao, C.-Q.;