An Atropos Biphenyl Bisphosphine Ligand with 2,2′-tert-Butylmethylphosphino Groups for the Rhodium-Catalyzed Asymmetric Hydrogenation of Enol Esters

Article abstract of DOI:10.1002/adsc.201800774

This is an update of our previous work concerning the development of Atropos biphenyl bisphosphine ligands. An unexpected Atropos structural property was confirmed by single crystal X-ray diffraction and this result is consistent with the computational calculations described in our previous work. This P-stereogenic bisphosphine ligand possessing a biphenyl backbone and 2,2′-tert-butylmethylphosphino groups has been applied to the Rh-catalyzed asymmetric hydrogenation of enol esters, which has not been widely studied and can be used for the synthesis of several important bioactive compounds. Although there is room for further improvement in enantioselectivity, the results reported herein provide a further understanding of such types of ligands. (Figure presented.).

Full text of DOI:10.1002/adsc.201800774

Title: An <i>Atropos</i> Biphenyl Bisphosphine Ligand with 2,2'-
<i>tert</i>-Butylmethylphosphino Groups for the Rhodium-
Catalyzed Asymmetric Hydrogenation of Enol Esters
Authors: Jia Jia, Dongyang Fan, Jian Zhang, Zhenfeng Zhang, and
Wanbin Zhang
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800774
Link to VoR: http://dx.doi.org/10.1002/adsc.201800774

10.1002/adsc.201800774
Advanced Synthesis & Catalysis
UPDATE
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
An Atropos Biphenyl Bisphosphine Ligand with 2,2'-tert-
Butylmethylphosphino Groups for the Rhodium-Catalyzed
Asymmetric Hydrogenation of Enol Esters
Jia Jia,a Dongyang Fan,b Jian Zhang,b Zhenfeng Zhang,b* and Wanbin Zhanga,b*
a
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering,
Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China
Tel&Fax: +86-21-54743265
E-mail: wanbin@sjtu.edu.cn
School of Pharmacy, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, P. R. China
b
E-mail: zhenfeng@sjtu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. This is an update of our previous work
concerning the development of Atropos biphenyl
bisphosphine ligands. An unexpected Atropos structural
property was confirmed by Single crystal X-ray diffraction
and this result is consistent with the computational
calculations described in our previous work. This P-
stereogenic bisphosphine ligand possessing a biphenyl
backbone and 2,2'-tert-butylmethylphosphino groups has
been applied to the Rh-catalyzed asymmetric
hydrogenation of enol esters, which has not been widely
studied and can be used for the synthesis of several
important bioactive compounds. Although there is room for
further improvement in enantioselectivity, the results
reported herein provide a further understanding of such
types of ligands.
Figure 1. Ligands bearing tert-butylmethylphosphino
groups with different backbones and ligands bearing
different 2,2'-substituents with biphenyl backbone.
Keywords: Atropos; Asymmetric hydrogenation; Biphenyl
bisphosphine ligand; P-Stereogenic; Rhodium
Our group has long focused on the development of
bidentate ligands with only two chiral 2,2'-
The development of chiral ligands with diverse
structures holds a prominent position in the field of
asymmetric catalysis.[1] As the earliest that were
developed, chiral bisphosphine ligands have received
great attention.[2] Several types of ligands possessing
different backbones and P-containing groups have
been designed, synthesized and applied in numerous
enantioselective transformations. In the last 20 years,
the development of P-stereogenic ligands has been
reignited, especially since the pioneering work of
Imamoto et al.[3-6] Taking ligands bearing tert-
butylmethylphosphino groups as typical examples,
BisP*, MiniPhos, QuinoxP*, BenzP*, etc, possessing
ethane, methane, quinoxaline, and benzene
backbones have been reported successively (Figure
1).[4] Despite these successes, the development of
new ligands bearing tert-butylmethylphosphino
groups on other types of backbone are still greatly
desired.
substituents on a biphenyl backbone. The tropos
bis(oxazoline) biphenyl ligand BiphBOX and
phosphine-oxazoline ligand BiphPHOX were
successively developed and successfully applied in
Cu-catalyzed asymmetric cyclopropanation, Pd-
catalyzed asymmetric allylation, and Ir-catalyzed
asymmetric hydrogenation.[7,8] Recently, we also
reported the biphenyl bisphosphine ligand BipheP*
bearing only 2,2'-tert-butylmethylphosphino groups.
(Figure 1).[9] From the NMR and computational
results, it can be speculated that the biphenyl axis has
a single configuration due to the large rotational
energy barrier and the significant free energy
difference between the two diastereoisomers caused
by the bulky chiral phosphino groups. Its unique
structure encouraged us to investigate its application
in the Rh-catalyzed asymmetric hydrogenation of
enamides. Soon after our publication, the Tang's
1
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
group and Boehringer Ingelheim Pharmaceuticals
synthesis for the preparation of optically active
pharmaceutical and agrochemical compounds (Figure
3).[13] However, due to the lower reactivity caused by
the weaker coordinating ability of the ester group, the
hydrogenation of such substrates has not been
thoroughly studied.
also
reported
a
series
of
biphenyl
dihydrobenzooxaphosphole ligands, BABIBOP or
BABIPhos, and disclosed the X-ray structures of their
Pd-, Rh-, and Cu-complexes.[10] The complexes
bearing these structurally novel ligands possess axial
chirality and showed high efficiency and excellent
enantioselectivities in asymmetric hydrogenations. In
order to further confirm the unique structure of such
ligands and extend their utilization, herein we report
the Single crystal X-ray diffraction of the free ligand
BipheP* and its performance in the Rh-catalyzed
asymmetric hydrogenation of enol esters. Such
reactions have not been widely studied and could be
useful for the synthesis of several important bioactive
compounds bearing a chiral α-hydroxy acid skeleton.
Figure 3. Selective examples of bioactive molecules
synthesized from chiral β-aryl α-hydroxy acids.
Table 1. Condition Optimization.
Figure 2. ORTEP drawing of BipheP* (dotted lines
represent the C-H··· interactions).
The compound BipheP* was synthesized from (S)-
tert-butylmethylphosphane-borane
and
1,2-
dibromobenzene via a simple route. Finally, a white
solid was obtained after crystallization from
methanol.[9] Recently, we have succeeded in
obtaining its absolute configuration by single crystal
X-ray diffraction (Figure 2).[11] This experimental
data is exactly the same as the previously calculated
result. The axial chirality of the ligand is exclusively
S-configuration. The dihedral angle of the two
benzene rings is 65, which is the same as that in the
simulated structure following minimum energy
optimization. The four C-H··· interactions exist with
a HtBu···CAr distance less than 3 Å, which lowers the
molecular energy and stabilizes the conformation.
Asymmetric hydrogenation is regarded as a practical
methodology due to its high efficiency and
environmental friendliness, and so has attracted much
attention from academia and industry.[12] In our initial
report, we found that the rhodium complex of
BipheP* is a highly active and enantioselective
catalyst for the asymmetric hydrogenation of β-aryl
enamides under mild conditions.[9] Considering the
same catalytic mechanism and similar stereocontrol
model, we believed that it could also be a potential
catalyst for the asymmetric hydrogenation of β-aryl
enol esters. This transformation has been
demonstrated to be one of the most feasible methods
for the preparation of chiral β-aryl α-hydroxy acids,
which comprise versatile building blocks in organic
Entrya) Solvent
Ligand
BipheP*
BipheP*
BipheP*
BipheP*
BipheP*
BipheP*
BipheP*
QuinoxP*
BenzP*
Conv (%)b) Ee (%)c)
1
2
THF
60
62
72
73
74
75
84
94
82
54
59
92
-
EtOAc
DCM
3
64
4
toluene
H2O
7
5
28
6
7d)
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
99
99
8
92
9
94
10
11
12
13
14
Me-DuPhos
ChiraPhos
BINAP
98
trace
trace
trace
trace
-
SegPhos
JosiPhos
-
-
a)
Substrate 1a (0.05 M), [Rh(BipheP*)(cod)]SbF6 or
[Rh(cod)2]SbF6/ligand (1 mol %), H2 (3 bar), solvent (2
b)
mL), rt, 24 h, unless otherwise noted. Conversions were
1
c)
calculated from H NMR spectra. The ee values were
determined by HPLC using chiral columns (Daicel IC-3). d)
Acetyl-substituted substrate 1a' was used instead of 1a.
2
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
Primarily, the hydrogenation of a model substrate 1a
was tested in different solvents (Table 1, entries 1-6).
In tetrahydrofuran (THF), ethyl acetate (EtOAc) and
dichloromethane (DCM), the reaction showed similar
results giving the desired product in approximately
60% conversion and 70% ee after 24 hours (entries 1-
3). When the transformation was conducted in
toluene or water, the conversion was dramatically
reduced because of the poor solubility for the
substrate (entries 4 and 5). However, the ee value
increased siginificantly in water to 84%. Much to our
delight, in the protic solvent methanol, the reaction
proceeded much more effectively, and the ee of the
hydrogenated product 2a reached 94%, significantly
better than other solvents (entry 6). We then changed
the benzoyl group to acetyl, but the ee of the obtained
product 2a' dropped down to 82% (entry 7). Other
important bisphosphine ligands, such as (R,R)-
QuinoxP*, (R,R)-BenzP*, (R,R)-Me-DuPhos, (S,S)-
ChiraPhos, (R)-BINAP, (R)-SegPhos and (Sp,R)-
JosiPhos, were also evaluated for the asymmetric
hydrogenation of 1a under the same conditions
(entries 8-14). Other electron-rich bisphosphine
ligands bearing tert-butylmethylphosphino groups
gave lower enantioselectivities (entries 8 and 9).
(S,S)-Me-DuPhos provided good results with 98%
conversion and 92% ee (entry 10). Using the ligands
bearing diphenylphosphine groups, very little of the
reduced product was obtained under the standard
conditions (entries 11-14).
ortho-chloro substituent, the ee values dropped
drastically to 31% and 37%, although the reactivity is
still high enough for complete conversion (1p and
1q). For other electron-withdrawing substituents,
such as
a
para-bromo group and para-
methoxycarbonyl group, lower reactivities were
observed under the same conditions and lower
enantioselectivities of 57% and 65% ee's were
obtained, respectively (1r and 1s).
Scheme 1. Substrate Scope.
Having established the optimized reaction conditions,
we then investigated the substrate scope for the
asymmetric hydrogenation (Scheme 1). For most of
the substrates, the reaction went to completion in 24
hours and with more than 90% ee. The para-methyl-
and meta-methyl-substituted substrates 1b and 1c
were hydrogenated to give the corresponding
products with similar results compared with that of
the model substrate 1a. The methoxy group, as a
more electron-donating substituent, exhibited a more
obvious position effect (1d-f). A methoxy group at
the meta position had a negative influence on the
reaction, while an ortho-methoxy group gave the
highest enantioselectivity for this reaction. An
opposite position effect was observed for the fluoro
group (1g-i). The meta-fluoro-substituted substrate
gave a similar result to that of the para-substituted
compound, while the ortho-fluoro-substituted
substrate gave its corresponding product with an
obviously lower enantioselectivity. Again, the
outcomes of para- and meta-chloro-substituted
substrates were almost identical (1j and 1k). Another
substrate 1l bearing a para-trifluoromethyl, and the 2-
naphthyl-substituted substrate 1m, also gave the
corresponding products with good enantioselectivities
of 90% and 92% ee's, respectively. We also tested
two disubstituted substrates 1n and 1o to give the
corresponding products with 90% and 94% ee,
respectively. Their products can be further converted
to Danshensu (Figure 4), which is a very important
bioactive compound.[13e] Surprisingly, for other ortho-
substituted substrates possessing an ortho-methyl or
We then studied the hydrogenation with a low
catalyst loading. The hydrogenation of substrate 1a
and 1o under 400/1 S/C gave complete conversion to
the desired product in 48 hours without loss of
enantiomeric excess. The applicability for this
reaction was also evaluated (Scheme 2). The
hydrogenated product 2a was easily hydrolyzed to β-
phenyl α-hydroxy acid 3a and smoothly cyclized to
4a, which can be further derivatized to the
enantiomer of a protein tyrosine phosphatase 1B
(PTP1B) inhibitor.[13b] The chiral product 2a can also
be directly reduced to chiral diol 5a and further
converted to a monoamine oxidase-B (MAO-B)
inhibitor named (R)-selegiline.[14]
3
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
Scheme 2. Further applications.
(R)-1-methoxy-1-oxo-3-(m-tolyl)propan-2-yl benzoate
1
(2c):[15a] Colorless oil, 29.2 mg, 98% yield. H NMR (400
MHz, CDCl3) δ 8.03 (d, J = 7.6 Hz, 2H), 7.57 (t, J = 7.6 Hz,
1H), 7.44 (t, J = 7.6 Hz, 2H), 7.20 (t, J = 7.6 Hz, 1H),
7.15-7.02 (m, 3H), 5.46-5.39 (m, 1H), 3.75 (s, 3H), 3.31-
3.18 (m, 2H), 2.33 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
170.15, 165.86, 138.06, 135.80, 133.30, 133.10, 130.13,
129.80, 129.31, 128.36, 127.78, 126.32, 73.52, 52.34,
37.47, 21.33. 94% ee (Daicel Chiralcel OJ-H column,
hexane/iPrOH = 85/15, 1.0 mL/min, λ = 220 nm, tR = 10.3
min, tS = 19.5 min.).
(R)-1-methoxy-3-(4-methoxyphenyl)-1-oxopropan-2-yl
benzoate (2d):[15a] Colorless oil, 30.5 mg, 97% yield. H
1
In summary, we have confirmed the atropos property
of BipheP* by single crystal X-ray diffraction. The
biphenyl axis possesses chirality which is induced by
the two chiral ortho-substituents. This result is
consistent with the previously reported computational
data. The application scope of this ligand has been
NMR (400 MHz, CDCl3) δ 8.03 (d, J = 7.6 Hz, 2H), 7.57 (t,
J = 7.6 Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.21 (d, J = 8.0
Hz, 2H), 6.85 (d, J = 8.0 Hz, 2H), 5.41 (t, J = 6.4 Hz, 1H),
3.78 (s, 3H), 3.74 (s, 3H), 3.30-3.16 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ 170.12, 165.86, 158.61, 133.30,
130.33, 129.80, 129.30, 128.38, 127.85, 113.90, 73.62,
55.18, 52.32, 36.69. 93% ee (Daicel Chiralcel IC-3 column,
hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS = 22.0
min, tR = 24.5 min.).
extended
to
the
Rh-catalyzed
asymmetric
hydrogenation of enol esters with high reactivities
and good enantioselectivities. We are continuing our
efforts to develop more ligands using this protocol
and to broaden the usage of these types of ligands.
(R)-1-methoxy-3-(3-methoxyphenyl)-1-oxopropan-2-yl
1
benzoate (2e):[15a] Colorless oil, 31.1 mg, 99% yield. H
NMR (400 MHz, CDCl3) δ 8.01 (d, J = 7.6 Hz, 2H), 7.55 (t,
J = 7.6 Hz, 1H), 7.43 (d, J = 7.6 Hz, 2H), 7.28-7.20 (m,
2H), 6.93-6.82 (m, 2H), 5.49 (t, J = 6.8 Hz, 1H), 3.84 (s,
3H), 3.75 (s, 3H), 3.42 (dd, J = 14.0, 8.8 Hz, 1H), 3.22 (dd,
J = 14.0, 8.8 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ
170.60, 165.94, 157.58, 133.16, 131.22, 129.78, 129.45,
128.46, 128.28, 124.06, 120.29, 110.17, 72.30, 55.21,
52.21, 32.51. 85% ee (Daicel Chiralcel OJ-H column,
hexane/iPrOH = 85/15, 1.0 mL/min, λ = 220 nm, tR = 21.5
min, tS = 23.5 min.).
Experimental Section
General procedure for asymmetric hydrogenation: the
enol ester (0.1 mmol), rhodium catalyst (0.001 mmol), and
a magnetic stirrer bar were charged in a hydrogenation
bottle and put in the autoclave. The system was evacuated
and filled with hydrogen. After repeating this operation
several times, degassed methanol (2 mL) was added and
the hydrogen pressure was adjusted to 3 bar. After
vigorous stirring for 24 hours, the volatile solvent was
evaporated under reduced pressure and the residue was
passed through a short column of silica gel. The solvent
was removed by evaporation and the product was dried in
vacuum. The enantiomeric excess of the product was
determined by HPLC using chiral columns.
(R)-1-methoxy-3-(2-methoxyphenyl)-1-oxopropan-2-yl
1
benzoate (2f):[15a] Colorless oil, 31.2 mg, 99% yield. H
NMR (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 2H), 7.55 (t,
J = 7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.21 (t, J = 8.0
Hz, 1H), 6.87 (d, J = 7.6 Hz, 1H), 6.83 (s, 1H), 6.77 (d, J =
8.4 Hz, 1H), 5.43 (t, J = 6.8 Hz, 1H), 3.74 (d, J = 7.2 Hz,
6H), 3.31-3.18 (m, 2H). 13C NMR (100 MHz, CDCl3) δ
170.05, 165.81, 159.63, 137.42, 133.32, 129.80, 129.48,
129.27, 128.38, 121.63, 114.90, 112.59, 73.37, 55.10,
52.37, 37.55. 96% ee (Daicel Chiralcel OJ-H column,
hexane/iPrOH = 85/15, 1.0 mL/min, λ = 220 nm, tR = 18.4
min, tS = 28.3 min.).
(R)-1-methoxy-1-oxo-3-phenylpropan-2-yl
benzoate
(2a):[15a] Colorless oil, 28.1 mg, 98% yield. H NMR (400
MHz, CDCl3) δ 8.02 (d, J = 8.0 Hz, 2H), 7.57 (t, J = 7.6
Hz, 1H), 7.44 (t, J = 7.6 Hz, 2H), 7.35-7.20 (m, 5H), 5.45
(dd, J = 8.0, 5.2 Hz, 1H), 3.75 (s, 3H), 3.37-3.21 (m, 2H).
13C NMR (100 MHz, CDCl3) δ 170.07, 165.84, 135.89,
133.31, 129.80, 129.30, 129.25, 128.50, 128.38, 127.06,
73.43, 52.36, 37.52. 94% ee (Daicel Chiralcel IC-3 column,
hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS = 13.8
min, tR = 14.6 min.).
1
(R)-3-(4-fluorophenyl)-1-methoxy-1-oxopropan-2-yl
1
benzoate (2g):[15a] Colorless oil, 29.7 mg, 98% yield. H
NMR (400 MHz, CDCl3) δ 8.00 (d, J = 7.6 Hz, 2H), 7.56 (t,
J = 7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.27-7.19 (m,
2H), 6.98 (t, J = 8.8 Hz, 2H), 5.45-5.38 (m, 1H), 3.72 (s,
3H), 3.32-3.17 (m, 2H). 13C NMR (100 MHz, CDCl3) δ
169.87, 165.76, 163.19 (160.74, d, J = 245 Hz), 133.40,
131.57 (131.53, d, J = 4 Hz), 130.86 (130.78, d, J = 8 Hz),
129.76, 129.16, 128.43, 115.49 (115.28, d, J = 21 Hz),
73.25, 52.39, 36.70. 93% ee (Daicel Chiralcel IC-3 column,
hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS = 12.5
min, tR = 13.6 min.).
(R)-1-methoxy-1-oxo-3-(p-tolyl)propan-2-yl
benzoate
(2b):[15a] Colorless oil, 29.5 mg, 99% yield. H NMR (400
MHz, CDCl3) δ 8.00 (d, J = 7.6 Hz, 2H), 7.54 (t, J = 7.6 Hz,
1H), 7.41 (t, J = 7.6 Hz, 2H), 7.15 (d, J = 7.6 Hz, 2H), 7.08
(d, J = 7.6 Hz, 2H), 5.38 (dd, J = 8.0, 5.2 Hz, 1H), 3.71 (s,
3H), 3.27-3.16 (m, 2H), 2.28 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 170.25, 165.99, 136.63, 133.35, 132.70, 129.78,
129.22, 129.19, 129.15, 128.38, 73.62, 52.35, 37.08, 20.99.
93% ee (Daicel Chiralcel OJ-H column, hexane/iPrOH =
85/15, 1.0 mL/min, λ = 220 nm, tR = 10.7 min, tS = 35.0
min.).
1
(R)-3-(3-fluorophenyl)-1-methoxy-1-oxopropan-2-yl
benzoate (2h): Colorless oil, 29.3 mg, 97% yield. 1H NMR
(400 MHz, CDCl3) δ 8.00 (d, J = 7.6 Hz, 2H), 7.55 (t, J =
7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.30-7.20 (m, 2H),
4
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
7.05 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 9.6 Hz, 1H), 6.92 (t, J
= 8.8 Hz, 1H), 5.51-5.40 (m, 1H), 3.73 (s, 3H), 3.35-3.18
(m, 2H). 13C NMR (100 MHz, CDCl3) δ 169.76, 165.74,
163.97 (161.52, d, J = 245 Hz), 138.36 (138.28, d, J = 8
Hz), 133.42, 130.03 (129.94, d, J = 9 Hz), 129.78, 129.11,
128.44, 124.97 (124.94, d, J = 3 Hz), 116.40 (116.18, d, J
= 22 Hz), 114.17 (113.96, d, J = 21 Hz), 73.00, 52.44,
(Daicel Chiralcel OJ-H column, hexane/iPrOH = 85/15,
1.0 mL/min, λ = 220 nm, tR = 9.8 min, tS = 12.2 min.).
(R)-1-methoxy-3-(naphthalen-2-yl)-1-oxopropan-2-yl
1
benzoate (2m):[15a] Colorless oil, 31.2 mg, 94% yield. H
NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.0 Hz, 2H), 7.84-
7.72 (m, 4H), 7.54 (d, J = 7.6 Hz, 1H), 7.48-7.37 (m, 5H),
5.55 (t, J = 6.8 Hz, 1H), 3.73 (s, 3H), 3.52-3.36 (m, 2H).
13C NMR (100 MHz, CDCl3) δ 170.09, 165.85, 133.43,
133.40, 133.33, 132.45, 129.81, 129.23, 128.38, 128.16,
128.07, 127.63, 127.56, 127.41, 126.12, 125.73, 73.42,
+
37.17. HRMS (ESI) calculated for C17H16FO4 [M+H]+
303.1027, found 303.1042. 92% ee (Daicel Chiralcel IC-3
column, hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS
= 11.5 min, tR = 13.1 min.). [α]D23 = +45 (c = 0.21, MeOH). 52.40, 37.68. 92% ee (Daicel Chiralcel OJ-H column,
hexane/iPrOH = 85/15, 1.0 mL/min, λ = 220 nm, tR = 24.5
min, tS = 98.3 min.).
(R)-3-(2-fluorophenyl)-1-methoxy-1-oxopropan-2-yl
benzoate (2i): Colorless oil, 28.9 mg, 96% yield. 1H NMR
(400 MHz, CDCl3) δ 8.00 (d, J = 7.6 Hz, 2H), 7.54 (t, J =
7.6 Hz, 1H), 7.41 (t, J = 7.6 Hz, 2H), 7.30-7.20 (m, 2H),
7.13-6.98 (m, 2H), 5.48-5.40 (m, 1H), 3.74 (s, 3H), 3.40-
3.25 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 169.88,
165.80, 162.52 (160.07, d, J = 245 Hz), 133.33, 131.54
(131.50, d, J = 4 Hz), 129.82, 129.15, 129.08 (129.00, d, J
= 8 Hz), 128.37, 124.10 (124.07, d, J = 3 Hz), 122.94
(122.79, d, J = 15 Hz), 115.53 (115.31, d, J = 22 Hz),
72.39, 52.43, 30.86 (30.83, d, J = 3 Hz). HRMS (ESI)
(R)-5-(2-(benzoyloxy)-3-methoxy-3-oxopropyl)-2-
methoxyphenyl benzoate (2n): White solid, 41.9 mg,
1
96% yield. M.p. 73-75 C. H NMR (400 MHz, CDCl3) δ
8.19 (d, J = 7.6 Hz, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.61 (t, J
= 7.6 Hz, 1H), 7.55 (t, J = 7.6 Hz, 1H), 7.49 (t, J = 7.6 Hz,
2H), 7.42 (t, J = 7.6 Hz, 2H), 7.15 (d, J = 8.4 Hz, 1H), 7.10
(s, 1H), 6.94 (d, J = 8.4 Hz, 1H), 5.42 (t, J = 6.4 Hz, 1H),
3.77 (s, 3H), 3.73 (s, 3H), 3.27-3.20 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ 169.98, 165.85, 164.59, 150.42,
139.78, 133.44, 133.31, 130.24, 129.87, 129.36, 129.28,
128.48, 128.40, 128.37, 127.55, 124.13, 112.51, 73.33,
+
calculated for C17H16FO4 [M+H]+ 303.1027, found
303.1028. 79% ee (Daicel Chiralcel IC-3 column,
hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS = 14.0
min, tR = 15.1 min.). [α]D23 = +10 (c = 0.17, MeOH).
+
55.93, 52.39, 36.60. HRMS (ESI) calculated for C25H23O7
[M+H]+ 435.1444, found 435.1443. 90% ee (Daicel
(R)-3-(4-chlorophenyl)-1-methoxy-1-oxopropan-2-yl
benzoate (2j): Colorless oil, 31.3 mg, 98% yield. 1H NMR
(400 MHz, CDCl3) δ 7.99 (d, J = 7.6 Hz, 2H), 7.56 (t, J =
7.6 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.30-7.16 (m, 4H),
5.42 (t, J = 6.4 Hz, 1H), 3.73 (s, 3H), 3.30-3.17 (m, 2H).
13C NMR (100 MHz, CDCl3) δ 169.79, 165.74, 134.34,
133.45, 133.00, 130.67, 129.77, 129.10, 128.68, 128.45,
73.05, 52.45, 36.83. HRMS (ESI) calculated for
Chiralcel IC-3 column, hexane/iPrOH = 95/5, 1.0 mL/min,
λ = 220 nm, tS = 59.7 min, tR = 74.3 min.). [α]D = +62 (c
= 0.14, MeOH).
23
(R)-4-(2-(benzoyloxy)-3-methoxy-3-oxopropyl)-2-
methoxyphenyl benzoate (2o): White solid, 42.5 mg, 98%
1
yield. M.p. 110-112 C. H NMR (400 MHz, CDCl3) δ
8.17 (d, J = 8.0 Hz, 2H), 8.04 (d, J = 7.6 Hz, 2H), 7.67-
7.37 (m, 6H), 7.07 (d, J = 7.9 Hz, 1H), 6.99-6.85 (m, 2H),
5.47 (t, J = 6.8 Hz, 1H), 3.75 (s, 6H), 3.35-3.23 (m, 2H).
13C NMR (100 MHz, CDCl3) δ 169.99, 165.77, 164.66,
151.14, 139.00, 134.87, 133.42, 130.24, 129.80, 129.33,
129.23, 128.52, 128.47, 128.42, 122.87, 121.61, 113.53,
73.28, 55.84, 52.45, 37.40. HRMS (ESI) calculated for
+
C17H16ClO4 [M+H]+ 319.0732, found 319.0746. 92% ee
(Daicel Chiralcel OJ-H column, hexane/iPrOH = 85/15,
1.0 mL/min, λ = 220 nm, tR = 12.9 min, tS = 19.8 min.).
[α]D23 = +26 (c = 0.13, MeOH).
(R)-3-(3-chlorophenyl)-1-methoxy-1-oxopropan-2-yl
benzoate (2k): Colorless oil, 31.5 mg, 99% yield. 1H NMR
(400 MHz, CDCl3) δ 8.00 (d, J = 7.6 Hz, 2H), 7.56 (t, J =
7.6 Hz, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.29 (s, 1H), 7.26-
7.19 (m, 2H), 7.18-7.13 (m, 1H), 5.42 (t, J = 6.4 Hz, 1H),
3.74 (s, 3H), 3.33-3.17 (m, 2H). 13C NMR (100 MHz,
CDCl3) δ 169.73, 165.73, 137.84, 134.24, 133.44, 129.79,
129.77, 129.60, 129.08, 128.45, 127.45, 127.33, 72.95,
+
C25H23O7 [M+H]+ 435.1444, found 435.1456. 94% ee
(Daicel Chiralcel IC-3 column, hexane/iPrOH = 95/5, 1.0
23
mL/min, λ = 220 nm, tS = 70.0 min, tR = 111.9 min.). [α]D
= +23 (c = 0.17, MeOH).
(R)-1-methoxy-1-oxo-3-(o-tolyl)propan-2-yl
benzoate
1
(2p)[15a]: Colorless oil, 29.1 mg, 98% yield. H NMR (400
MHz, CDCl3) δ 7.72 (d, J = 7.6 Hz, 2H), 7.50 (t, J = 7.6 Hz,
1H), 7.42 (t, J = 7.6 Hz, 2H), 7.23-7.04 (m, 4H), 5.06 (q, J
= 7.6 Hz, 1H), 3.72 (s, 3H), 3.34-3.14 (m, 2H), 2.36 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 172.56, 166.89,
136.77, 134.19, 133.75, 131.75, 130.63, 129.80, 128.57,
127.24, 126.96, 125.97, 52.74, 52.37, 35.73, 19.35. 31% ee
(Daicel Chiralcel OJ-H column, hexane/iPrOH = 85/15,
1.0 mL/min, λ = 220 nm, tR = 50.0 min, tS = 53.4 min.).
(R)-3-(2-chlorophenyl)-1-methoxy-1-oxopropan-2-yl
benzoate (2q): Colorless oil, 30.9 mg, 97% yield. 1H NMR
(400 MHz, CDCl3) δ 8.01 (d, J = 8.0 Hz, 2H), 7.54 (t, J =
7.6 Hz, 1H), 7.47-7.29 (m, 4H), 7.22-7.13 (m, 2H), 5.53-
5.47 (m, 1H), 3.75 (s, 3H), 3.55-3.31 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ 170.03, 165.81, 134.38, 133.68,
133.33, 131.53, 129.83, 129.68, 129.13, 128.64, 128.36,
126.80, 72.08, 52.47, 35.09. HRMS (ESI) calculated for
+
52.46, 37.11. HRMS (ESI) calculated for C17H15ClNaO4
[M+Na]+ 341.0551, found 341.0553. 93% ee (Daicel
Chiralcel IC-3 column, hexane/iPrOH = 95/5, 1.0 mL/min,
23
λ = 220 nm, tS = 11.9 min, tR = 13.3 min.). [α]D = +33 (c
= 0.22, MeOH).
(R)-1-methoxy-1-oxo-3-(4-
(trifluoromethyl)phenyl)propan-2-yl benzoate (2l):[15a]
1
Colorless oil, 34.8 mg, 99% yield. H NMR (400 MHz,
CDCl3) δ 7.99 (d, J = 7.6 Hz, 2H), 7.56 (d, J = 8.0 Hz, 3H),
7.46-7.36 (m, 4H), 5.48 (t, J = 6.4 Hz, 1H), 3.74 (s, 3H),
3.41-3.26 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 169.64,
165.68, 140.00, 133.49, 129.93 (129.61, 129.29, 128.97, q,
J = 32 Hz), 129.76, 129.67, 129.03, 128.47, 128.13
(125.43, 122.72, 120.01, q, J = 271 Hz), 125.51 (125.47,
125.44, 125.40, q, J = 4 Hz), 72.79, 52.49, 37.21. 90% ee
+
C17H16ClO4 [M+H]+ 319.0732, found 319.0729. 37% ee
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201800774
Advanced Synthesis & Catalysis
(Daicel Chiralcel OJ-H column, hexane/iPrOH = 85/15,
1.0 mL/min, λ = 220 nm, tR = 13.2 min, tS = 16.2 min.).
[α]D23 = +17 (c = 0.27, MeOH).
(R)-3-phenylpropane-1,2-diol (5a):[15d] A solution of
LiAlH4 in THF (10.0 eq, 1.4 mL, 1M) was added dropwise
to 2a (39.8 mg, 0.14 mmol) at 0 C under N2. The mixture
was allowed to warm to room temperature and stirred
overnight. The resulting suspension was cooled to 0 °C and
then the LiAlH4 was quenched by addition of EA (2 mL)
and diluted HCl (4 mL, 10%). The organic layer was dried
over MgSO4, filtered and evaporated. Pure product was
obtained by column chromatography as a colorless oil in
97% yield (20.6 mg) and with 90% ee (Daicel Chiralcel
IC-3, hexane/iPrOH = 90/10, 1.0 mL/min, λ = 210 nm, 25
(R)-3-(4-bromophenyl)-1-methoxy-1-oxopropan-2-yl
1
benzoate (2r):[15a] Colorless oil, 11.8 mg, 32% yield. H
NMR (400 MHz, CDCl3) δ 7.99 (d, J = 7.6 Hz, 2H), 7.55
(d, J = 7.6 Hz, 1H), 7.42 (t, J = 8.0 Hz, 4H), 7.15 (d, J =
8.0 Hz, 2H), 5.43 (t, J = 6.4 Hz, 1H), 3.72 (s, 3H), 3.30-
3.15 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 169.77,
165.72, 134.86, 133.45, 131.63, 131.03, 129.77, 129.09,
128.45, 121.11, 72.96, 52.45, 36.89. 57% ee (Daicel
Chiralcel OJ-H column, hexane/iPrOH = 85/15, 1.0
mL/min, λ = 220 nm, tR = 12.8 min, tS = 14.3 min.).
1
C, tR = 11.1 min, tS = 12.2 min.). H NMR (400 MHz,
CDCl3) δ 7.38-7.13 (m, 5H), 3.96-3.84 (m, 1H), 3.63 (dd, J
= 11.2, 2.4 Hz, 1H), 3.46 (dd, J = 11.2, 7.2 Hz, 1H), 3.11
(s, 2H), 2.81-2.66 (m, 2H).
methyl
(R)-4-(2-(benzoyloxy)-3-methoxy-3-
oxopropyl)benzoate (2s): Colorless oil, 28.0 mg, 82%
1
yield. H NMR (400 MHz, CDCl3) δ 8.02-7.94 (m, 4H),
7.55 (t, J = 7.6 Hz, 1H), 7.42 (t, J = 7.6 Hz, 2H), 7.35 (d, J
= 7.6 Hz, 2H), 5.47 (t, J = 6.4 Hz, 1H), 3.87 (s, 3H), 3.72
(s, 3H), 3.39-3.26 (m, 2H). 13C NMR (100 MHz, CDCl3) δ
169.72, 166.81, 165.70, 141.19, 133.45, 129.81, 129.76,
129.38, 129.04, 128.44, 72.84, 52.47, 52.07, 37.42. HRMS
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21572131 and 21620102003), Shanghai
Municipal Education Commission (201701070002E00030), and
Science and Technology Commission of Shanghai Municipality
(15JC1402200). We also thank the Instrumental Analysis Center
of SJTU for characterization.
+
(ESI) calculated for C19H19O4 [M+H]+ 311.1283, found
311.1293. 65% ee (Daicel Chiralcel IC-3 column,
hexane/iPrOH = 95/5, 1.0 mL/min, λ = 220 nm, tS = 52.7
min, tR = 58.2 min.). [α]D23 = +43 (c = 0.44, MeOH).
(R)-2-hydroy-3-phenylpropanoic acid (3a):[15b] The
solution of hydrogenated product 2a (70.0 mg, 0.24 mmol)
in concentrated HCl (15 mL) was heated to reflux for 8
hours. After cooling down to room temperature, the
reaction was extracted with DCM (15 mL × 3). After
drying over MgSO4, the solvent was evaporated and the
pure product was isolated by column chromatography
using DCM then DCM/MeOH (10/1) as eluent to obtain a
white solid in 94% yield (37.6 mg) and with 93% ee
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
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10.1002/adsc.201800774
Advanced Synthesis & Catalysis
UPDATE
An Atropos Biphenyl Bisphosphine Ligand with
2,2'-tert-Butylmethylphosphino Groups for the
Rhodium-Catalyzed Asymmetric Hydrogenation of
Enol Esters
Adv. Synth. Catal. Year, Volume, Page – Page
Jia Jia, Dongyang Fan, Jian Zhang, Zhenfeng
Zhang,* and Wanbin Zhang*
8
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