Asymmetric induction in the addition of enantiomerically pure H-phosphinate to chiral aldimines: diastereoselective generation of α-amino phosphinates with P,C-stereogenic centers

Article abstract of DOI:10.1016/j.tetasy.2016.06.022

α-Amino phosphinates with P,C-stereogenic centers were prepared from a P-retained addition of (R_P)-(?)-menthyl H-phenylphosphinate to (R)-aldimines with up to 86:14 dr under catalyst and solvent free condition at ambient temperature; the single

Full text of DOI:10.1016/j.tetasy.2016.06.022

Tetrahedron: Asymmetry xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Asymmetric induction in the addition of enantiomerically pure
H-phosphinate to chiral aldimines: diastereoselective generation
of a-amino phosphinates with P,C-stereogenic centers
Meng Yang, Hao Xu, Zhong-Yang Zhou, He Zhang, Li-Juan Liu, Yong-Ming Sun, Shao-Zhen Nie,
⇑
Chang-Qiu Zhao
College of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, China
a r t i c l e i n f o
a b s t r a c t
Article history:
a
-Amino phosphinates with P,C-stereogenic centers were prepared from a P-retained addition of
Received 24 April 2016
Accepted 30 June 2016
Available online xxxx
(RP)-(ꢀ)-menthyl H-phenylphosphinate to (R)-aldimines with up to 86:14 dr under catalyst and solvent
free condition at ambient temperature; the single (SP,S -C)-stereoisomers were isolated in moderate
a
yields. Chirality on the nitrogen of chiral aldimine was proposed to control the stereoselectivity, and
the (ꢀ)-menthoxyl showed mismatched asymmetric induction with (S)-aldimines.
Ó 2016 Elsevier Ltd. All rights reserved.
1. Introduction
non-chiral aldimines was examined. a-Amino phosphinates with P,
C-stereogenic centers were obtained under catalyst and solvents-
free conditions at ambient temperature. Although the chirality of
the title compounds was controlled by stereogenic amine, rather
than by (RP)-1a, the latter exhibited matched or mismatched
induction effects with (R)- or (S)-chiral amine, respectively.
a
-Amino phosphoric acid derivatives, especially stereogenic
ones, have attracted much attention due to their widely pharmaco-
logical applications such as antibacterial action, enzyme inhibitors,
HIV protease, herbicides, fungicides, plant growth regulators,
antithrombotic agents, peptidases, and peptidase and protease
inhibitors.1–8 These compounds also have potential as auxiliaries
and ligands,9 or as precursors, in asymmetric catalysis.10 Many
2. Results and discussion
research groups are committed to acquiring stereogenic
a-amino
2.1. Addition of (RP)-1a to (R)-1-phenylethanimines 2
phosphoric derivatives.11 The developed approaches include Man-
nich type reactions of aldehydes/ketones, amines, and H-phos-
phites,12 and nucleophilic additions of H-phosphites to imines13
catalyzed by aluminum salalen complexes, chiral thioureas,
binol-derived phosphoric acids and others.14 Although several
When a mixture of (RP/SP)-1a/1a0 (50:50) was used to react with
(R)-2a, which was generated from benzaldehyde and (R)-1-phe-
nylthanamine, four stereoisomers were formed (Scheme 1). On
31P NMR spectra, the corresponding peaks were observed at
38.18, 37.88, 37.47 and 36.22 ppm, in the ratio of 10:39:11:40.
reviews have documented the preparation of a-amino phosphoric
derivatives,15 the synthesis of those that have P-stereogenic, espe-
cially P,C-stereogenic centers, has scarcely been involved.16
As reported, the chiral imines which were derived from (S)- or
(R)-1-phenylethylamine reacted with P-H species to effectively
However, (RP)-1a only afforded SP,S -C-3aA (36.22 ppm) and SP,R
a
a-
C-3aB (38.18 ppm) in a ratio of 80:20 via a P-retention reaction
(vide infra). Thus, the two other peaks at 37.88 and 37.47 ppm
were assigned as 3aC and 3aD which was generated from (SP)-1a0.
In a separate experiment, 1a/1a0 (90:10) reacted with (R)-2a
and gave four peaks in a ratio of 16:6:6:72 (Fig. 1). Among those,
the 72:16 ratio of 3aA/3aB was near to the above 40:10. The
88:12 ratio of 3aA + 3aB/3aC + 3aD was near to the original ratio
of 1a/1a0. From the 1H NMR spectra, the corresponding ratio of
the four stereoisomers could also be distinguished.20
induce the formation of new C-stereogenic centers in
a-amino
phosphoric derivatives.17 However, when P-stereogenic P-H spe-
cies are used in the reaction, to the best of our knowledge, their
inducting behavior has scarcely been studied.18,19 Herein the reac-
tion of (RP)-(ꢀ)-menthyl H-phenylphosphinate 1a18d with chiral or
The reaction of (R)-2a with 1a under various conditions was
investigated (Table 1). Under neat conditions at 80 °C, 3aA and
⇑
Corresponding author. Tel.: +86 635 8239659; fax: +86 635 8239121.
E-mail address: literabc@hotmail.com (C.-Q. Zhao).
http://dx.doi.org/10.1016/j.tetasy.2016.06.022
0957-4166/Ó 2016 Elsevier Ltd. All rights reserved.
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2
M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
O
O
H
O
P
H
N
P (S)
P (S)
N
(R)
Ph
Ph
Ph
(R)
(R)
RO
Ph
RO
(S)
+
H
RO
Ph
Ph
Ph
Ph
(RP)-1a
3a
(SP,Sα-C)-
A
3a
(SP,Rα-C)-
80oC
B
Ph
N
Ph
+
O
O
H
O
P
yield >99%
H
N
P (R)
P ( R)
N
(R)
Ph
Ph
RO
(R)
(R)
(S)
Ph
H
+
RO
Ph
RO
Ph
Ph
Scheme 1. The reaction of 1a or 1a/1a0 with (R)-2a.
83:17 drC (entry 10). The drC were significantly improved after
recrystallization, and in most cases the single stereoisomers were
isolated in moderate yields.
The crystallography of 3aA, 3bA, 3dA and 3iA unambiguously
showed the (S)-configurations on both phosphorus and
a-carbon
(Fig. 2).22 The retained configuration on the phosphorus was thus
confirmed. Since both 3aA and 3aB were generated from 1a, the
(SP,R -C)-structure was confirmed for 3aB. When a mixture of
a
1a/1a0 (50:50) was used to react with (R)-2a, 3aD/3aC were formed
from (SP)-1a0 in 78:22 drC, and the dominant 3aD was similarly sup-
posed to have an (S)-configuration on the
a-carbon. Thus, the
peaks at 37.88 and 37.47 ppm on 31P NMR spectra, among the four
ones in Figure 1 and Scheme 1 (also seen in entry 1 of Table 4),
were assigned as (RP,S -C)-3aD (major) and (RP,R -C)-3aC (minor),
a
a
respectively.
In most cases, the peaks of 3A were located at the upper field
compared with 3B on the 31P NMR spectra. However, the peak of
SP,S -C-3iA, whose structure was confirmed by X-ray diffraction,
a
was located at downfield than 3iB (entry 9 of Table 2). The reversed
peaks location might be due to the ortho-hydroxyl of salicy-
laldimine that took part in the formation of the chain structure.
As shown in Part C and D of Figure 2, the nitrogen located near
to P@O in 3A, perhaps formed an intramolecular hydrogen bond.
The presence of an ortho-hydroxyl in 3iA/3iB resulted in the
variation of magnetic environment around the phosphorus.
Figure 1. Selected peaks of 3aA, 3aB, 3aC and 3aD on 31P NMR (a) and 1H NMR (b)
spectra for the reaction of (RP/SP)-1a/1a0 (90:10) with (R)-2a.
Table 1
Hydrophosphorylation of 2a with 1a or 1a/1a0
Entry
Catalyst
(mol %)
Temp/time
(°C/hr)
Solvent
Yield (%)a,b
drC (drP)a,b
3aB were formed in an 80:20 ratio and >99% yield (drC: the
diastereomeric ratio on phosphorus and on a-carbon, respectively,
1
2
3
4
5
6
7
8
No
No
No
No
No
No
No
rt/12
60/12
80/3
90/3
80/5
45/12
45/12
rt/12
60/12
60/12
45/12
45/12
rt/12
rt/12
rt/12
80/0.5
80/0.5
No
No
No
No
Trace
67
/
entry 3). The formation of 3aC and 3aD was not detected. Thus, the
drP was assigned as >99:1. Reducing the temperature led to the
incomplete conversion of 1a. For example, at 60 °C, 1a was con-
sumed in 67% after 12 h (entry 2). At room temperature, only trace
amounts of 3a were detected (entry 1). However, a higher temper-
ature, such as 90 °C, resulted in a loss of chirality on phosphorus, as
observed (97:3 drP) for the formation of 3aA-3aD (entry 4). Running
the reaction in a solution or using an alkali catalyst did not afford
3a (entries 5–13). Acidic catalysts, such as TsOH, showed weak
activity, and 3a was formed in poor yields (entries 14–15). By com-
paring entries 16 and 17, the presence of a radical initiator obvi-
ously accelerated the reaction, which indicated that the free
radical seemed to be involved in the reaction.21
The reactions of various aldimines (R)-2 were examined under
neat conditions at 80 °C (Table 2). In most entries, compounds 3
were obtained in near complete yields. Compound (R)-2 containing
methoxyl, hydroxyl and halides reacted smoothly with 1a (entries
4, 5–9). It seemed that electron donating groups on (R)-2 could give
better selectivity, as seen when 3b to 3d were formed in obviously
higher drC than others (entry 2–4). Aliphatic aldimines such as
(R)-2j also reacted with 1a to afford 3j in 83% yield and
78:22
80:20 (>99:1)
80:20 (97:3)
/
/
/
/
/
/
/
/
/
>99
>99
NA
NA
NA
NA
NA
NA
NA
NAc
NAc
21
EtOH
THF
DMSO
No
THF
DMSO
THF
DMSO
DMSO
No
Na2CO3 (20)
K2CO3 (20)
K2CO3 (20)
K2CO3 (100)
K2CO3 (100)
KOH (20)
TsOH (50)
TsOH (100)
AIBN
9
10
11
12
13
14
15
16
17
77:23
76:24
79:21d
78:22d
No
No
No
31
62
37
No
a
The reactions were carried out with 1a (dr >99:1) (1 mmol) and (R)-2a
(1 mmol) in the presence of catalyst (if applicable) in some solvents (2 ml, if
applicable).
The yield and dr were estimated by 31P NMR spectra based on 1a. The drC were
b
assigned as 3aA/3aB and drP (in parenthesis) as 3aA + 3aB:3aC + 3aD.
c
Phenylphosphinic acid was detected.
A mixture of 1a/1a0 was used, and the two stereoisomers 3aA and 3aB were
confirmed based on Figure 1.
d
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M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
3
Table 2
Preparation of (SP,S -C)-3A and (SP,R -C)-3B
a
a
O
H
O
P (S)
O
P
H
N
80oC
neat
P (S)(S)
N Ph
(R)
R1
N
Ph
Ph
(R)
RO
Ph
(R)
RO
Ph
+
H
+
RO
Ph
R1
R1
3
(SP,Rα-C)-
B
3
(RP)-1a
(SP,Sα-C)-
2
A
Entry
R1 of (R)-2
Yield % (dr)a
Isolated yield % (dr)b
1
2
3
4
5
6
7
8
9
10
Ph, 2a
>99 (80:20)
>99 (83:17)
>99 (86:14)
>99 (85:15)
>99 (80:20)
97 (80:20)
97 (75:15)
98 (80:20)
>99 (77:23)
83 (83:17)
3aA, 56 (>99:1)
3bA, 60 (>99:1)
3cA, 63 (>99:1)
p-MeC6H4, 2b
p-iPrC6H4, 2c
p-MeOC6H4, 2d
p-ClC6H4, 2e
m-BrC6H4, 2f
o-FC6H4, 2g
o-BrC6H4, 2h
o–HOC6H4, 2i
iPr, 2j
3dA, 65 (>99:1)
3eA/3eB, 55 (84:16)
3fA/3fB, 54 (81:19)
3gA, 56 (>99:1)
3hA, 52 (>99:1)
3iA, 48 (>99:1)
3jA/3jB, 57 (85:15)
a
1a and (R)-2 were heated 80 °C for 8 h. The crude products were directly analyzed with 31P NMR spectra, and the yield and dr were estimated. The drP values obtained
were >99:1 because of the P-stereospecific addition (vide infra). The drC in the table were assigned as 3A/3B.
b
The products were isolated by recrystallization with dichloromethane/hexane.
2.2. Proposed stereochemistry for the addition of H-P species to
aldimines
menthoxyl of (SP)-1a0 gave similar dr to t-butoxyl of 1d (in 39:11
or 78:22 dr). We supposed that the bigger alkoxyl groups tended
to enhance the interaction (a) of Figure 3 and the asymmetric
When aldimines 4, which were derived from non-chiral amines
were used to the addition, 1a was also entirely consumed. How-
ever, two stereoisomers of adduct 5 were formed in a ratio of
approximately 50:50 (Table 3). On the basis of the similarly
retained configuration on phosphorus, 5A and 5B were supposed
induction of chiral imine. L-Menthoxyl of (RP)-1a showed the
stronger enhancement than other alkoxyl groups. A discussion
about the volume of menthoxyl or alkoxyl in phenylphosphinates
could also be found in our previous publication.24
The induction of L-menthoxyl to the selective formation of a-
to have an (S)-configuration on the
a
-carbon, and an (S)- or (R)-
amino phosphoric derivatives was also found in the reported reac-
tions of (R)-2 or (S)-20 with P-symmetric di- or trimenthoxyl phos-
phites.17b–d Recently, Ordoñez et al. reported an improved
selectivity, up to 93:7 dr, by employing the more bulky (S)-3,3-
dimethyl-2-butylamine as chiral source, in a one-pot process
utilizing non-chiral dimethyl phosphites, chiral amines and
aldehydes.17e They studied the conformation of imines and
proposed the major diastereomers were afforded from the re face
attacking from the less hindered side to the imines by phosphite.
In addition to Ordoñez’s proposal, as we supposed, the flexible
configuration of the nitrogen should be alternatively considered
configuration on phosphorus, respectively.
Relatively poor drC values of 3A0/3B were also observed for the
0
reaction of 1a with (S)-20 that was derived from (S)-1-phenylethy-
lamine (Scheme 2). When 1a/1a0 (ca 69:31) was used to react with
(S)-2d0, the two peaks originated from (SP)-1a0 were also observed
31
in the ratio near 1:1 on P NMR spectra, which indicated (SP)-1a0
0
0
also afforded the two stereoisomers 3C /3D in poor selectivity.
From the results of Tables 2 and 3, and Scheme 2, it was inferred
that the ratio of 3A/3B (as well as aforementioned 3D/3C) was con-
trolled by chiral aldimine, rather by stereogenic phosphorus.
Although the stereogenic phosphorus of 1a did not contribute to
the selectively of the formations of the two stereoisomers, it was
noteworthy that the L-menthoxyl showed mismatched asymmetric
induction to (S)-aldimine.
The stereochemistry of the addition is proposed in Figure 3, in
which the conformation of 3A and 3B were referred to X-ray diffrac-
tion structures (Fig. 2). The strong repulsion (a) between the lone
for the selective formation of
a-amino phosphoric derivatives. As
can be seen in entries 1–5 in Table 2, (R)-2 containing electron
donating groups gave better drC than those containing electron
withdrawing groups. The spatial interaction between aryl and chi-
ral amine moiety should be similar in the two types of (R)-2. The
electron donating group-substituted
a-aryl possessing increased
electron cloud density, might enhance the repulsion with the lone
pair of electrons of the nitrogen, and result in a bigger stability-dif-
ference between 3A and 3B. Conversely, the long distance but
matched or mismatched asymmetric induction between men-
thoxyl to chiral aldimine indicated that the configuration of nitro-
gen controlled the stabilities of 3A and 3B. The DFT calculation also
indicated 3aA was more stable than 3aB by 1.339 Kcal/mol (for
details, please see SI).
pair of electrons of the nitrogen to
a-aryl in 3B (or 3C, the minor
stereoisomer) was supposed to result in its lower stability, and
therefore, less formation. Thus, the ratio of 3A/3B (or 3D/3C)
depended on the possible ratio of (RN)/(SN) which was controlled
by chiral carbon skeleton of (R)-2. When (RP)-1a was reacted with
(S)-20, the interaction (b) between
a-aryl to o-isopropyl of 3B
0
0
0
became significant. Thus, 3A and 3B showed the similarly stabili-
ties, and the selectivity for the formation of them was quite poor.23
Petnehazya et al. reported the dominant formation of two
stereoisomers during the addition of ethyl phenylphosphinate 1c
to chiral imines.17a In order to further investigate the induction
behaviors, the reaction of H-phosphinates having various alkoxyl
groups with (R)-2a was examined (Table 4). The four
stereoisomers were similarly formed, in a ratio of (SC)-3:(RC)-3 of
72:28 to 78:22 [the two dominant ones were assigned as (SC)-
stereoisomers]. The alkoxyl groups of 1 slightly influenced the
selectivity. For example, the methoxyl and ethoxyl of 1b and 1c
seemed to give worse dr than others (entries 2 and 3). The
Compared to the catalytic reactions for the preparation of
a-amino phosphorus derivatives, our procedure employed two
types of auxiliaries that were inexpensive and can be conveniently
removed by means of the well-established procedure, avoiding the
usage of expensive metallic catalyst or chiral ligands. Petnehazya
et al. reported the stereoselective preparation of
phosphinic acids from the hydrolysis of N-1-phenylethyl ethyl
-amino phosphinate (the compound same to our entry 3 of
a-amino
a
Table 4) with concentrated HCl in glacial acetic acid. The following
N-deprotection was realized via Pd/C catalyzed hydrogenolysis, in
20–60% yield and with good to excellent er.17a,25 On the basis of
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4
M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
Figure 2. ORTEP drawing for 3aA (A) and 3iA (B), one-dimensional chain structures for 3aA (C) and 3iA (D).
their procedure, our products 3 would be similarly converted into
-amino phosphinic acids. Due to the hydrolysis, the reported
(R)-aldimine. Non-chiral aldimine, as well as the reaction of
(RP)-1a with (S)-aldimine, did not show selectivity. On the basis
a
P-inversed substitution of another auxiliary (ꢀ)-menthoxyl with
nucleophilic reagents, such as alkyl,26 amino,27 and alkoxyl,28
accomplished the P-deprotection and stereoselective conversion
of the products to various P,C-stereogenic compounds.
of these results, the configuration of the
supposed to be controlled by chiral aldimines via strong repulsion
between the lone electron pair of nitrogen to -aryl groups. The
menthoxyl in (RP)-1a enhanced the asymmetric induction of chiral
aldimines. In the reaction of (RP)-1a with (S)-aldimines, the
mismatched induction was caused by the interaction between
a-carbon atom was
a
3. Conclusion
ortho-isopropyl of menthyl to a-aryl.
In conclusion, P,C-stereogenic
a-amino phosphinates were pre-
pared from stereogenic aldimines and H-phosphinate (RP)-1a in
4. Experimental
high 86:14 drC. In most cases, the single (SP,S -C)-stereoisomers
a
were isolated in moderate yields. The reactions were carried out
under neat conditions, which were simple, convenient,
environmentally friendly, and therefore practical. The P-retention
mechanism was confirmed. During the reaction of (RP)-1a with
4.1. General procedure for synthesis of a-aminophosphinates
Under nitrogen, (RP)-1a (280 mg, 1 mmol)18d and aldimine
(1 mmol) were added in a flask, the mixture was stirred for 8 h
at 80 °C. The crude product was obtained as a pale yellow solid.
(R)-aldimine, the chirality on the
a-carbon was induced by
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M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
5
Table 3
The addition of 1a to 4
O
H
N
O
P
O
H
N
80oC
P ( S)
R1
N
P (S)
+
(R)
+
RO
Ph
R2
(S)
H
RO
R =
R2
R2
RO
Ph
yield >99%
Ph
R1
R1
1a
-menthyl;
4a-h
5
A/5B (ca. 50:50)
L
R1 = Ph, p-MeC6H4, p-iPrC6H4, p-MeOC6H4;
R
2 = nBu, tBu
Entry
R1
R2
(dr)a
Isolated yield % (dr)b
1
2
3
4
5
6
7
8
Ph
tBu
tBu
tBu
tBu
nBu
nBu
nBu
nBu
5aA/5aB, 45:55
5bA/5bB, 53:47
5cA/5cB, 50:50
5dA/5dB, 49:51
5eA/5eB, 37:63
5fA/5fB, 53:47
5gA/5gB, 40:60
5hA/5hB, 57:43
89 (44:56)
85 (54:46)
85 (47:53)
81 (47:53)
80 (40:60)
87 (52:48)
82 (43:57)
86 (57:43)
p-MeC6H4
p-iPrC6H4
p-MeOC6H4
Ph
p-MeC6H4
p-iPrC6H4
p-MeOC6H4
a
Yield and dr were estimated by 31P NMR spectra, dr were assigned as 5A/5B. The structures of 5A and 5B were determined based on peaks in the upfield and downfield
regions of the 31P NMR spectra, respectively.
b
The products were isolated by recrystallization with dichloromethane/hexane.
After recrystallization with petroleum ether and dichloromethane,
the resulting solid was filtered and dried in vacuo.
(dd, J = 7.5, 3.1 Hz, 2H), 7.29 (s, 1H), 7.26 (s, 1H), 7.19 (dd, J = 15.3,
7.6 Hz, 5H), 7.12–7.02 (m, 2H), 4.18 (dd, J = 13.1, 8.8 Hz, 1H), 4.03
(d, J = 14.5 Hz, 1H), 3.51 (q, J = 6.4 Hz, 1H), 2.34 (s, 3H), 1.94 (br,
1H), 1.61 (d, J = 12.0 Hz, 1H), 1.52 (d, J = 10.7 Hz, 1H), 1.42–1.28
(m, 2H), 1.27–1.11 (m, 2H), 1.02 (d, J = 6.4 Hz, 3H), 0.94–0.78 (m,
2H), 0.71 (dd, J = 22.4, 9.5 Hz, 4H), 0.63 (d, J = 7.0 Hz, 3H), 0.48 (d,
J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 36.01 (s). 13C NMR
(101 MHz, CDCl3) d 145.8 (s), 137.3 (s), 133.8 (d, J = 5.3 Hz), 132.6
(d, J = 9.2 Hz), 131.9 (d, J = 2.7 Hz), 128.9 (s), 129.0 (s), 129.1 (s),
128.5–127.9 (m), 126.9 (d, J = 13.6 Hz), 61.0 (s), 59.8 (s), 55.1 (d,
J = 12.4 Hz), 49.1 (d, J = 5.5 Hz), 43.3 (s), 34.3 (s), 31.6 (s), 24.8 (s),
22.7 (s), 22.0 (d, J = 7.7 Hz), 21.3 (d, J = 4.7 Hz), 15.4 (s). Calcd for
4.2. (SP,S -C)-L-Menthyl [(R)-1-phenylethylaminophenyl methyl]
a
phenylphosphinate 3aA
White solid (274 mg, 56%, >99:1 drC), mp 176–179 °C; 1H NMR
(400 MHz, CDCl3) d 7.88–7.74 (m, 2H), 7.56 (t, J = 6.9 Hz, 1H), 7.46
(dt, J = 7.4, 3.4 Hz, 2H), 7.34–7.12 (m, 8H), 7.12–7.02 (m, 2H), 4.19
(qd, J = 11.1, 4.6 Hz, 1H), 4.07 (d, J = 14.7 Hz, 1H), 3.52 (q, J = 6.4 Hz,
1H), 2.17–2.12 (m, 1H), 1.65 (s, 1H), 1.62 (s, 1H), 1.60–1.09 (m, 6H),
1.05 (d, J = 6.5 Hz, 3H), 1.01–0.60 (m, 7H), 0.49 (d, J = 6.9 Hz, 3H).
31P NMR (162 MHz, CDCl3) d 36.22 (s). 13C NMR (101 MHz, CDCl3)
d 145.6 (s), 137.0 (d, J = 3.0 Hz), 133.5 (s), 132.6 (d, J = 9.3 Hz),
132.1 (t, J = 15.2 Hz), 129.2 (d, J = 5.7 Hz), 128.6–128.0 (m), 127.7
(d, J = 2.5 Hz), 127.0 (d, J = 19.0 Hz), 61.3 (s), 60.2 (s), 55.3 (d,
J = 12.3 Hz), 49.0 (d, J = 5.6 Hz), 43.3 (s), 34.2 (s), 31.6 (s), 24.9 (s),
22.7 (s), 22.1 (d, J = 2.7 Hz), 21.4 (s), 15.4 (s). Calcd for C31H40NO2-
P: C, 76.04; H, 8.23. Found: C, 75.79; H, 8.18.
C32H42NO2P: C, 76.31; H, 8.41. Found: C, 75.86; H, 8.33.
4.4. (SP,S -C)- -Menthyl [(R)-1-phenylethylamino-p-isopropyl
L
a
phenylmethyl]phenylphosphinate 3cA
White solid (335 mg, 63%, >99:1 drC), mp 160–164 °C; 1H NMR
(400 MHz, CDCl3) d 7.80 (dd, J = 10.5, 7.6 Hz, 2H), 7.54 (t, J = 7.4 Hz,
1H), 7.44 (td, J = 7.4, 3.3 Hz, 2H), 7.16 (dt, J = 14.4, 7.6 Hz, 7H), 7.04
(d, J = 6.3 Hz, 2H), 4.16 (dt, J = 15.0, 11.0 Hz, 1H), 4.02 (d,
J = 14.3 Hz, 1H), 3.49 (q, J = 6.4 Hz, 1H), 2.89 (dt, J = 13.7, 6.9 Hz,
1H), 2.00 (br, 1H), 1.62 (d, J = 11.4 Hz, 1H), 1.61–1.21 (m, 10H),
1.21–1.04 (m, 2H), 1.01 (d, J = 6.5 Hz, 3H), 0.82 (ddd, J = 35.0,
26.4, 10.0 Hz, 2H), 0.73–0.60 (m, 6H), 0.45 (d, J = 6.9 Hz, 3H). 31P
4.3. (SP,S -C)-L-Menthyl [(R)-1-phenylethylamino-p-tolylmethyl]
a
phenylphosphinate 3bA
White solid (302 mg, 60%, >99:1 drC), mp 170–174 °C; 1H NMR
(400 MHz, CDCl3) d 7.84–7.75 (m, 2H), 7.54 (t, J = 7.4 Hz, 1H), 7.46
Table 4
The diastereomeric ratio for the reaction of (R)-2a with 1
O
P
O
P
O
H
N
H
N
80oC
( S)
(R) Ph
Ph
(R)
(R)
P
Ph
N
Ph
RO
Ph
RO
Ph
+
H
+
RO
Ph
neat
Ph
Ph
2a
(R)-
3
1a
(SC)-
3
(RC)-
Entry
R
SC-3:RC-3a
1
2
3
4
5
6
Men, 1a/1a0
Me, 1b
Et, 1c
iPr, 1d
tBu, 1e
cHex, 1f
(40 + 39):(10 + 11)b
73:27
72:28
78:22
76:24
75:25
a
The ratio were estimated by 31P NMR spectra. For 1b to 1f, the two higher peaks located at down field were assigned as (SC)-3, and the two lower ones were assigned as
(RC)-3.
b
The ratio of (SP,SC)-3aA + (RP,SC)-3aD:(SP,RC)-3aB + (RP,RC)-3aC.
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6
M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
O
H
O
P ( S)
O
P
H
N
80oC
P (S)
N Ph
(S)
R1
N
Ph
(S)
Ph
RO
Ph
(R)
(S)
RO
Ph
+
H
+
RO
Ph
(RP)-1a
R = -menthyl;
>99%
R1
R1
2a'- 2d'
3 ' 3
'
(ca. 50:50)
/
A
B
L
R1 = Ph, p-ClC6H4, p-iPrC6H4, p-MeOC6H4;
Scheme 2. The reaction of 1a with (S)-20.
H
H
Ph
Ph
Me
Ph
Ph
Me
N
H
O
P
N
H
O
P
H
H
.
.
iPr
H
.
.
iPr
Ar
O
Me
Me
O
(a)
Ar
H
3
A (SP,SC
)
3
B (SP,RC) less stable
H
H
Ph
O
Me
Ph
O
Me
N
H
Ph
P
N
H
Ph
H
H
iPr
H
.
.
iPr
.
.
Ar
O
P
H
Me
Me
O
(a)
Ar
3
D (RP,SC
)
3
C (RP,RC) less stable
H
H
H
H
Ph
O
Me
Ph
Me
(b)
Ph
Ar
Ph
H
H
.
.
.
.
iPr
iPr
H
Ar
O
Me
Me
O
O
(a)
H
3A' (SP,SC) less stable
3B' (SP,RC) less stable
H
H
H
Ph
Me
Ph
Ph
Me
(b)
O
O
H
H
.
.
.
iPr
iPr
Ar
.
H
H
Me
Me
O
Ph
O
(a)
Ar
H
3D' (RP,SC) less stable
3C' (RP,RC) less stable
0
Figure 3. Supposed conformation for 3A–3B and 3A0–3D
.
NMR (162 MHz, CDCl3) d 36.10 (s). 13C NMR (101 MHz, CDCl3) d
148.0 (d, J = 2.6 Hz), 145.6 (s), 134.0 (d, J = 2.9 Hz), 133.7 (s),
132.5 (s), 132.4 (s), 132.3 (s), 131.7 (d, J = 2.7 Hz), 128.9 (d,
J = 5.8 Hz), 128.1 (s), 127.8 (d, J = 12.3 Hz), 126.7 (d, J = 11.6 Hz),
126.2 (d, J = 1.6 Hz), 60.6 (s), 59.5 (s), 55.0 (d, J = 12.5 Hz), 48.8
(d, J = 5.7 Hz), 43.1 (s), 34.1 (s), 33.8 (s), 31.4 (s), 24.7 (s), 24.0 (s),
22.5 (s), 21.9 (s), 21.1 (s), 15.2 (s). Calcd for C34H46NO2P: C,
76.80; H, 8.72. Found: C, 76.75; H, 8.60.
(101 MHz, CDCl3) d 159.4 (d, J = 2.4 Hz), 145.7 (s), 133.6 (s), 132.6
(s), 132.5 (s), 132.0 (d, J = 2.7 Hz), 130.2 (d, J = 5.8 Hz), 128.9 (d,
J = 3.2 Hz), 128.4 (s), 128.–127.9 (m), 126.9 (d, J = 15.7 Hz), 113.8
(d, J = 1.5 Hz), 60.6 (s), 59.5 (s), 55.4 (s), 55.2 (d, J = 12.3 Hz), 49.1
(d, J = 5.5 Hz), 43.3 (s), 34.3 (s), 31.6 (s), 24.9 (s), 22.7 (s), 22.1 (d,
J = 5.9 Hz), 21.4 (s), 15.5 (s). Calcd for C32H42NO3P: C, 73.96; H,
8.15. Found: C, 75.79; H, 8.07.
4.6. (SP)-L-Menthyl [(R)-1-phenylethylamino-p-chlorophenyl
4.5. (SP,S -C)-
L-Menthyl [(R)-1-phenylethylamino-p-methoxyl
methyl]phenylphosphinate 3eA/3eB
a
phenylmethyl]phenylphosphinate 3dA
White solid (288 mg, 55%, 84:16 drC), mp White solid; mp 165–
169 °C; 1H NMR (400 MHz, CDCl3) d 7.83–7.74 (m, 2H), 7.73–7.62
(m, 1H), 7.57 (t, J = 7.4 Hz, 1H), 7.50–7.39 (m, 3H), 7.28–7.13 (m,
10H), 7.03 (d, J = 5.8 Hz, 2H), 4.34–4.24 (m, 0.16H), 4.18 (d,
J = 11.2 Hz, 0.84H), 4.01 (d, J = 14.9 Hz, 1H), 3.45 (q, J = 6.4 Hz,
1H), 2.04 (s, 1H), 1.62 (s, 4H), 1.53 (d, J = 11.1 Hz, 3H), 1.33 (s,
1H), 1.27–1.11 (m, 2H), 1.05 (d, J = 6.5 Hz, 3H), 0.85 (d, J = 6.9 Hz,
2H), 0.77–0.63 (m, 9H), 0.51 (d, J = 6.9 Hz, 3H). 31P NMR
(162 MHz, CDCl3) d 35.57 (s, 16%), 34.38 (s, 84%). 13C NMR
(101 MHz, CDCl3) d 145.2 (s), 135.6 (s), 133.4 (s), 133.1–132.2
White solid (338 mg, 65%, >99:1 drC), mp 159–162 °C; 1H NMR
(400 MHz, CDCl3) d 7.78 (dd, J = 11.1, 7.1 Hz, 2H), 7.54 (t, J = 6.9 Hz,
1H), 7.44 (td, J = 7.4, 3.3 Hz, 2H), 7.19 (p, J = 6.5 Hz, 5H), 7.08–7.02
(m, 2H), 6.81 (d, J = 8.6 Hz, 2H), 4.18 (dd, J = 7.0, 4.1 Hz, 1H), 4.01
(d, J = 14.3 Hz, 1H), 3.80 (s, 3H), 3.51 (q, J = 6.3 Hz, 1H), 1.88 (br,
1H), 1.62 (d, J = 12.0 Hz, 1H), 1.53 (d, J = 11.9 Hz, 2H), 1.42 (dd,
J = 8.1, 5.7 Hz, 1H), 1.28–1.11 (m, 4H), 1.04 (d, J = 6.5 Hz, 3H),
0.88 (dt, J = 11.8, 9.3 Hz, 2H), 0.68 (t, J = 7.4 Hz, 6H), 0.51 (d,
J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 36.08 (s). 13C NMR
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M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
7
(m), 132.1 (s), 130.3 (d, J = 5.6 Hz), 128.8 (s), 128.6–127.9 (m),
127.0 (s), 126.7 (s), 60.7 (s), 59.6 (s), 55.6 (d, J = 11.7 Hz), 48.9 (d,
J = 5.4 Hz), 43.2 (s), 34.0 (s), 31.5 (d, J = 10.1 Hz), 24.8 (s), 22.6 (d,
J = 18.3 Hz), 22.1 (s), 21.9 (s), 21.0 (s), 15.2 (s). Calcd for
0.60 (d, J = 7.0 Hz, 3H), 0.42 (d, J = 6.8 Hz, 3H). 31P NMR
(162 MHz, CDCl3) d 35.63 (s). 13C NMR (101 MHz, CDCl3) d 145.2
(s), 137.0 (s), 132.4 (m, J = 18.8, 9.1 Hz), 130.2 (d, J = 3.8 Hz),
129.0 (s), 128.3 (d, J = 12.6 Hz), 127.8 (d, J = 2.3 Hz), 127.1 (s),
126.8 (s), 126.0 (d, J = 7.6 Hz), 104.4 (s), 103.9 (s), 102.7 (d,
J = 7.2 Hz), 77.5 (s), 64.0 (d, J = 1.7 Hz), 59.0 (s), 57.9 (s), 55.9 (d,
J = 13.3 Hz), 49.0(d, J = 5.7 Hz), 43.1 (s), 34.1 (s), 31.5 (s), 29.9 (s),
24.6 (s), 22.6 (s), 22.3 (s), 22.0 (s), 21.4 (s), 18.8 (s), 18.2 (d,
J = 13.7 Hz), 15.5 (s), 15.2 (s). Calcd for C31H39BrNO2P: C, 65.49;
H, 6.91. Found: C, 65.27; H, 6.84.
C31H39ClNO2P: C, 71.05; H, 7.50. Found: C, 70.86; H, 7.42.
4.7. (SP)- -Menthyl [(R)-1-phenylethylamino-m-bromophenyl
L
methyl]phenylphosphinate 3fA/3fB
White solid (307 mg, 54%, 81:19 drC), mp 166–168 °C; 1H NMR
(400 MHz, CDCl3) d 7.84–7.75 (m, 2H), 7.56 (t, J = 6.8 Hz, 1H), 7.52–
7.43 (m, 3H), 7.39 (dd, J = 13.1, 4.8 Hz, 2H), 7.30 (dd, J = 7.5, 3.7 Hz,
1H), 7.26 (s, 1H), 7.24–7.07 (m, 6H), 7.07–6.95 (m, 3H), 4.32 (dd,
J = 6.7, 4.2 Hz, 0.19H), 4.25–4.12 (m, 0.81H), 3.98 (d, J = 14.6 Hz,
0.81H), 3.73 (d, J = 18.1 Hz, 0.19H), 3.56–3.50 (m, 0.19H), 3.46 (q,
J = 6.4 Hz, 0.81H), 2.20 (s, 1H), 1.68–1.58 (m, 2H), 1.53 (d,
J = 11.6 Hz, 2H), 1.43 (s, 1H), 1.41–1.33 (m, 1H), 1.31 (d,
J = 6.6 Hz, 1H), 1.28–1.13 (m, 2H), 1.03 (t, J = 8.5 Hz, 3H), 0.99–
0.91 (m, 1H), 0.87 (ddd, J = 18.8, 10.6, 7.5 Hz, 2H), 0.79–0.63 (m,
8H), 0.50 (d, J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 37.32 (s,
19%), 35.41 (s, 81%). 13C NMR (101 MHz, CDCl3) d 145.1 (s), 144
(s), 140 (d, J = 2.9 Hz), 138.6 (s), 133.1 (s), 133.0–131.8 (m), 131.5
(d, J = 5.1 Hz), 130.8–129.8 (m), 129.6 (m, J = 9.4, 2.2 Hz), 128.8
(s), 128.5 (s), 128.4–127.9 (m), 127.9–127.3 (m), 127.0 (d,
J = 12.4 Hz), 126.7 (s), 122.3 (s), 122.3 (s), 122.3 (s), 61.7 (s), 60.9
(s), 60.7 (s), 59.8 (s), 55.7 (d, J = 11.7 Hz), 55.3 (d, J = 14.5 Hz),
49.0 (dd, J = 17.6, 5.7 Hz), 43.2 (d, J = 10.8 Hz), 34.1 (d, J = 8.5 Hz),
31.5 (d, J = 11.9 Hz), 25.4 (s), 24.9 (d, J = 3.9 Hz), 22.8 (s), 22.5 (s),
22.4–22.3 (m), 22.0 (dd, J = 23.8, 21.3 Hz), 21.3 (s), 15.5 (s), 15.1
(s). Calcd for C31H39BrNO2P: C, 65.49; H, 6.91. Found: C, 65.23; H,
6.81.
4.10. (SP,S -C)-L-Menthyl [(R)-1-phenylethylamino-o-hydroxy
phenylmethyl]phenylphosphinate 3iA
a
White solid (243 mg, 48%, >99:1 drC), mp 194–198 °C; 1H NMR
(400 MHz, CDCl3) d 10.05 (s, 1H), 7.69 (dd, J = 11.2, 7.6 Hz, 2H), 7.56
(t, J = 7.4 Hz, 1H), 7.43 (td, J = 7.5, 3.5 Hz, 2H), 7.26 (s, 1H), 7.24–
7.17 (m, 2H), 7.17–7.04 (m, 3H), 6.83 (d, J = 8.1 Hz, 1H), 6.71 (dt,
J = 14.5, 7.3 Hz, 2H), 4.31 (dt, J = 15.1, 11.0 Hz, 1H), 4.15 (d,
J = 16.1 Hz, 1H), 3.56 (q, J = 6.6 Hz, 1H), 2.44 (s, 1H), 1.70 (dd,
J = 17.6, 10.4 Hz, 2H), 1.63–1.52 (m, 2H), 1.36–1.21 (m, 2H), 1.16
(d, J = 6.5 Hz, 3H), 1.05–0.83 (m, 3H), 0.71 (dd, J = 6.7, 2.8 Hz, 6H),
0.59 (d, J = 6.9 Hz, 3H). 31P NMR (162 MHz, CDCl3) d 40.36 (s). 13C
NMR (101 MHz, CDCl3) d 157.1 (d, J = 4.1 Hz), 144.3 (s), 132.7 (s),
132.6 (s), 132.5 (s), 131.1 (d, J = 7.1 Hz), 129.9 (s), 129.3 (s), 128.4
(s), 128.1 (d, J = 12.7 Hz), 127.2 (s), 126.6 (s), 120.8 (s), 119.5 (s),
118.8 (s), 62.2 (s), 61.1 (s), 55.5 (d, J = 12.8 Hz), 48.8 (d,
J = 5.3 Hz), 43.1 (s), 34.0 (s), 31.5 (s), 25.2 (s), 22.6 (s), 21.9 (s),
21.0 (s), 20.6 (s), 15.1 (s). Calcd for C31H40NO3P: C, 73.64; H, 7.97.
Found: C, 73.49; H, 7.88.
4.11. (SP)-L-Menthyl [(R)-1-phenylethylamino-2-methylpropyl]
phenylphosphinate 3jA/3jB
4.8.
(SP,S -C)-
L-Menthyl
[(R)-1-phenylethylamino-o-fluro
a
phenylmethyl]phenylphosphinate 3gA
White solid (260.0 mg, 57%, 85:15 drC), mp 194–198 °C; 1H
NMR (400 MHz, CDCl3) d 7.83 (dd, J = 23.6, 15.3 Hz, 2H), 7.60–
7.51 (m, 1H), 7.47 (dd, J = 13.1, 10.2 Hz, 2H), 7.23–7.11 (m, 3H),
6.98 (d, J = 6.2 Hz, 2H), 4.30–4.16 (m, 0.85H), 4.14 (d, J = 6.4 Hz,
0.15H), 3.52 (d, J = 6.3 Hz, 1H), 2.85 (d, J = 13.9 Hz, 1H), 2.37–2.11
(m, 2H), 1.92 (d, J = 6.5 Hz, 1H), 1.74–1.48 (m, 4H), 1.36 (t,
J = 10.0 Hz, 1H), 1.26 (dd, J = 21.4, 12.7 Hz, 2H), 1.10 (d, J = 6.4 Hz,
3H), 1.05–0.62 (m, 21H). 31P NMR (162 MHz, CDCl3) d 41.24 (s,
15%), 39.83 (s, 85%). 13C NMR (101 MHz, CDCl3) d 145.6 (s), 145.0
(d, J = 7.0 Hz), 135.4 (d, J = 5.6 Hz), 134.3 (d, J = 5.5 Hz), 133.9 (s),
133.1–131.9 (m), 131.9 (s), 128.8–127.9 (m), 127.7 (d, J = 3.5 Hz),
127.1 (s), 127.1 (s), 127.0 (s), 60.3–59.3 (m), 59.3–57.2 (m), 56.8–
56.4 (m), 56.4 (s), 49.4 (dd, J = 10.4, 4.8 Hz), 43.5 (s), 34.26 (s),
31.9–31.5 (m), 29.9 (s), 28.6 (t, J = 21.3 Hz), 28.3 (s), 25.7–24.6
(m), 24.6 (s), 24.3 (d, J = 8.8 Hz), 22.8 (t, J = 5.9 Hz), 22.6–21.9
(m), 21.9–21.5 (m), 21.4 (d, J = 3.7 Hz), 17.9–17.3 (m), 16.0–15.20
(m). Calcd for C28H42NO2P: C, 73.81; H, 9.29. Found: C, 73.62; H,
9.20.
White solid (284 mg, 56%, >99:1 drC), mp 175–178 °C; 1H NMR
(400 MHz, CDCl3) d 7.87 (dd, J = 11.2, 7.5 Hz, 2H), 7.56 (q, J = 6.8 Hz,
2H), 7.48 (td, J = 7.4, 3.3 Hz, 2H), 7.23 (dd, J = 13.0, 6.8 Hz, 1H),
7.19–7.10 (m, 4H), 7.01 (dd, J = 9.1, 3.3 Hz, 2H), 6.95 (d, J = 8.9 Hz,
1H), 4.55 (d, J = 15.4 Hz, 1H), 4.19–4.09 (m, 1H), 3.47 (q,
J = 6.6 Hz, 1H), 2.16 (br, 1H), 1.60 (d, J = 12.4 Hz, 1H), 1.50 (dd,
J = 10.1, 3.1 Hz, 2H), 1.25 (d, J = 5.5 Hz, 1H), 1.24–1.10 (m, 3H),
1.01 (d, J = 6.4 Hz, 3H), 0.94–0.80 (m, 2H), 0.67 (d, J = 6.5 Hz, 3H),
0.60 (d, J = 7.0 Hz, 3H), 0.42 (d, J = 6.8 Hz, 3H). 31P NMR
(162 MHz, CDCl3) d 35.61 (d, J = 4.9 Hz). 13C NMR (101 MHz, CDCl3)
d 162.5 (d, J = 6.3 Hz), 160.1 (d, J = 6.3 Hz), 145.4 (s), 133.7 (s),
132.4 (d, J = 9.5 Hz), 132.2 (d, J = 2.6 Hz), 130.0 (s), 129.1 (d,
J = 6.0 Hz), 128.5–127.7 (m), 127.1 (d, J = 4.5 Hz), 126.8 (s), 124.7
(d, J = 15.1 Hz), 124.4 (s), 115.1 (s), 114.8 (s), 55.8 (d, J = 12.8 Hz),
53.9–52.5 (m), 51.8 (d, J = 114.6 Hz), 48.9 (d, J = 5.6 Hz), 43.2 (s),
34.2 (s), 31.6 (s), 29.9 (s), 24.7 (s), 22.6 (s), 22.4–21.8 (m), 21.3
(d, J = 4.8 Hz), 15.3 (s). Calcd for C31H39FNO2P: C, 73.35; H, 7.74.
Found: C, 73.26; H, 7.65.
Acknowledgments
4.9.
(SP,S -C)-
L
-Menthyl
[(R)-1-phenylethylamino-o-bromo
a
The authors acknowledge the financial support of the Natural
Science Foundation of China (grant no. 20772055) and Natural
Science Foundation of Shandong Province (grant no.
ZR2014BP007).
phenylmethyl]phenylphosphinate 3hA
White solid (296 mg, 52%, >99:1 drC), mp 169–173 °C; 1H NMR
(400 MHz, CDCl3) d 7.87 (dd, J = 11.2, 7.5 Hz, 2H), 7.56 (q, J = 6.8 Hz,
2H), 7.48 (td, J = 7.4, 3.3 Hz, 2H), 7.23 (dd, J = 13.0, 6.8 Hz, 1H),
7.19–7.10 (m, 4H), 7.01 (dd, J = 9.1, 3.3 Hz, 2H), 6.95 (d, J = 8.9 Hz,
1H), 4.55 (d, J = 15.4 Hz, 1H), 4.19–4.09 (m, 1H), 3.47 (q,
J = 6.6 Hz, 1H), 2.16 (s, 1H), 1.60 (d, J = 12.4 Hz, 1H), 1.50 (dd,
J = 10.1, 3.1 Hz, 2H), 1.25 (d, J = 5.5 Hz, 1H), 1.24–1.10 (m, 3H),
1.01 (d, J = 6.4 Hz, 3H), 0.94–0.80 (m, 2H), 0.67 (d, J = 6.5 Hz, 3H),
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.tetasy.2016.06.
022.
Please cite this article in press as: Yang, M.; et al. Tetrahedron: Asymmetry (2016), http://dx.doi.org/10.1016/j.tetasy.2016.06.022

8
M. Yang et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
16. (a) Bhadury, P. S.; Song, B. A.; Yang, S.; Zhang, Y.; Zhang, S. Curr. Org. Synth.
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Please cite this article in press as: Yang, M.; et al. Tetrahedron: Asymmetry (2016), http://dx.doi.org/10.1016/j.tetasy.2016.06.022